Formulations used for the treatment of substrate surfaces

ABSTRACT

The invention relates to formulations containing at least one nitrogen-free polysiloxane compound, at least one polyamino polysiloxane and/or polyammonium polysiloxane compound, and/or at least one amino polysiloxane and/or ammonium polysiloxane compound, and an optional silicone-free cationic surfactant, a coacervate phase-forming agent, and carrier substances. Also disclosed are a method for the production of the inventive formulations and the use thereof for treating natural and synthetic fibrous materials.

The invention relates to formulations based on polysiloxane, toprocesses for their preparation and to their use, especially for thetreatment of textiles and other natural and synthetic fiberlikematerials.

Amino-containing polysiloxanes are known as textile softeners (EP441530). The introduction of amino structures modified by ethyleneoxide/propylene oxide units as side chains brings about an improvementin the effect (U.S. Pat. No. 5,591,880, U.S. Pat. No. 5,650,529). Inthis context, the alkylene oxide units allow the controlled adjustmentof the hydrophilic-hydrophobic balance.

It has likewise been proposed to react α,ω-epoxy-modified siloxanes withα,ω-amino-functionalized alkylene oxides, and to use these products ashydrophilic softeners (U.S. Pat. No. 5,807,956, U.S. Pat. No.5,981,681).

To improve the substantivity, experiments on the introduction ofquaternary ammonium groups into alkylene oxide-modified siloxanes havebeen undertaken.

Branched alkylene oxide-modified polysiloxane quats (“polysiloxanequats”=quaternary ammonium-containing polysiloxanes) have beensynthesized by condensation from α,ω-OH-terminated polysiloxanes andtrialkoxysilanes. The quaternary ammonium structure is introduced viathe silane, and the quaternary nitrogen atom is substituted by alkyleneoxide units (U.S. Pat. No. 5,602,224).

Strictly comb-type alkylene oxide-modified polysiloxane quats havelikewise been described. The hydroxyl groups of polyethersiloxanessubstituted in a comblike manner are converted using epichlorohydrin(U.S. Pat. No. 5,098,979) or chloroacetic acid (U.S. Pat. No. 5,153,294,U.S. Pat. No. 5,166,297) to the corresponding chlorine derivatives.Subsequently, quaternization is effected with tertiary amines.

U.S. Pat. No. 6,242,554 describes α,ω-difunctional siloxane derivatives,each of which have a separate quaternary ammonium and alkylene oxideunit. These materials feature improved compatibility with polarenvironments.

The reaction of α,ω-diepoxides with tertiary amines in the presence ofacids affords α,ω-diquaternary siloxanes which can be used for haircarepurposes (DE-A-37 19 086). In addition to tetraalkyl-substitutedquaternary ammonium structures, aromatic imidazolium derivatives arealso claimed.

A reduction in the washout from hair can be achieved when theα,ω-diepoxides are reacted with tertiary diamines in the presence ofacids to give long-chain polyquaternary polysiloxanes (EP-A-282 720).Aromatic quaternary ammonium structures are not disclosed.

Such polyquaternary imidazolium derivatives are considered in U.S. Pat.No. 6,240,929. These cationic compounds are said to have a furtherincreased compatibility toward the anionic surfactants present incosmetic formulations. However, the washout resistance from hair relatesto the brief attack of principally water and very mild surfactants whichdo not irritate the skin, while wash-resistant hydrophilic softeners fortextiles have to resist the attack of concentrated surfactant solutionswith high grease and soil dissolution capacity. An additionalcomplicating factor is that modern detergents comprise highly alkalinecomplexing agents, oxidative bleaches and complex enzyme systems, andthe fibers are often exposed to their action at elevated temperaturesover a period of hours.

Highly charged, very hydrophilic synthetic polycationic compounds arelikewise capable of improving the compatibility with anionic surfactantsystems (U.S. Pat. No. 6,211,139) or of associating with fibers in thepresence of solutions of anionic surfactants (WO 99/14300). The latterdocument also describes polyimidazolium derivatives inter alia. Mixturesof cationic polysaccharide derivatives with polysiloxanes have likewisebeen investigated (J. V. Gruber et al., Colloids and Surfaces B:Biointerfaces 19 (2000) 127-135).

It is also known that hydrocarbon-based quats which are usedextensively, for example, in fabric softeners can be combined withpolysiloxanes.

For instance, it has been proposed to emulsify silicone oils of certainviscosities with cationic surfactants and to incorporate these emulsionsinto fabric softener formulations which comprise further cationicsurfactants (WO 00/71806 and WO 00/71807). In U.S. Pat. No. 4,961,753,hydrocarbon quats are combined with a mixture of high viscosity and lowviscosity polysiloxanes.

Emulsions of hydrocarbon-based quats (silicone-free quaternary ammoniumcompounds with hydrocarbon radicals) with highly branched or crosslinkedpolydimethylsiloxane (PDMS) are claimed in U.S. Pat. No. 4,908,140.According to U.S. Pat. No. 4,978,462, it is advantageous also to addstraight-chain PDMS to such a system.

The combination of hydrocarbon-based quats with OH-terminatedpolysiloxanes as a textile softener is claimed in WO 98/50502.

Combinations of hydrocarbon-based quats with siloxanes from the group ofthe unfunctionalized polydimethylsiloxanes, aminosiloxanes orpolyethersiloxanes are described in WO 95/24460 as constituents offabric softener formulations.

According to U.S. Pat. No. 5,852,110 and U.S. Pat. No. 6,090,885,aminosiloxane emulsions are prepared by alkaline polymerization in thepresence of cationic surfactants.

Finally, GB 1 549 180 discloses the combination of emulsions ofunfunctionalized polysiloxanes obtained by alkaline polymerization inthe presence of cationic surfactants with further hydrocarbon quat.Alternatively, it is also said to be possible to use thehydrocarbon-based quats together with α,ω-diquaternary polysiloxanes orpolyquaternary polysiloxanes or aminosiloxanes substituted in a comblikemanner.

None of the proposals considered constitutes a satisfactory solution tothe problem of achieving the soft hand, possible in principle by the useof silicones, of textile materials directly during the wash process withmodern heavy-duty and light-duty detergent systems based on anionicsurfactants.

WO 02/10256, WO 02/10257 and WO 02/10259 claim silicone materials whichenable softening of textiles during the wash process with laundrydetergent systems of this type. The US laid-open specification2002/0103094 considers the use of the silicone materials mentioned intextile care formulations.

A further improvement in the performance of the above-described siloxanesystems with regard to the achievable softness of the treated fibers,especially in the case of equal or improved substantivity (adhesion ofthe siloxane systems to the fiber), the flexibility in the formulationof the siloxane systems and the administration form, especially with aview to a reduction of the use amounts needed and the material costs, isvery desirable.

It is thus an object of the invention to provide formulations based onpolysiloxane, especially for the treatment of textiles and other naturaland synthetic fiberlike materials, for example paper fibers and hair,which impart to such materials or substrates, preferably textilematerials, a softness typical of silicones, an improved elasticity andreduced creasing tendency, especially in the presence of anionicsurfactants or other ionic surface-active compositions for fiberpretreatment, as occur, for example, in the case of use in laundrydetergent systems and in the case of finishing of pretreated fibers. Atthe same time, the formulations should have a high substantivity on thesubstrate surfaces.

It is a further object of the invention to provide for the use of theseformulations as a constituent of separate softener systems after thewashing of fibers has been performed, as a constituent of softenersystems for nonwovens such as paper and textiles, as a constituent ofsystems for initial textile finishing, as an ironing aid and compositionfor prevention and reversal of textile creases and as a constituent ofcosmetic systems for the treatment of hair and skin.

It is a further object of the invention to provide formulations based onpolysiloxane which can be adjusted flexibly to the type of thesubstrates to be treated and the treatment conditions by simplevariation of the composition ratios of the components present. Inaddition, the formulations should enable the amounts required to achievethe desired properties of the substrates to be treated and/or the use ofexpensive polysiloxane components, for example polysiloxane quats, to bereduced without a worsening in the desired properties of the substratesto be treated occurring.

It has been found that, surprisingly, particular multicomponentformulations of especially polysiloxane-containing compounds achieve theabove object and constitute inexpensive and nevertheless exceptionallyeffective agents for the treatment of particular materials, inparticular fiber materials.

The present invention thus provides a formulation which comprises:

-   -   a) at least one nitrogen-free polysiloxane compound,    -   b) at least one polyamino- and/or polyammonium-polysiloxane        compound b1) and/or at least one amino- and/or        ammonium-poly-siloxane compound b2)    -   c) optionally one or more silicone-free surfactants,    -   d) optionally one or more coacervate phase formation agents,    -   e) optionally one or more carrier substances.

The inventive formulation preferably contains, based on the total amountof components a) and b), from 5 to 99% by weight of component a) andfrom 1 to 95% by weight of component b). More preferably, the amount ofcomponent a) is from 20 to 90% by weight and the amount of component b)is from 10 to 80% by weight; particularly preferably the amount ofcomponent a) is from 30 to 90% by weight and the amount of component b)is from 10 to 70% by weight, based in each case on the total amount ofcomponents a) and b).

The optionally present carrier substances of component e) are preferablyselected from solid carrier substances f) and/or liquid carriersubstances g), which are described more precisely below.

The inventive formulation preferably contains from 0 to 1500, morepreferably from 0 to 1000, more preferably from 0 to 500, even morepreferably from 0 to 300 and most preferably from 0 to 150, parts byweight of the optionally present components c), d) and e), based on 100parts by weight of components a) and b).

Component c) is added preferably in amounts of from 0 to 70, morepreferably from 0 to 50 and particularly preferably from 0 to 30, partsby weight per 100 parts by weight of the total amount of components a)and b). If component c) is present in the inventive formulation, it ispresent in amounts of >0 part by weight, preferably >0.1 part by weight,per 100 parts by weight of the total amount of components a) and b).

Component d) is added preferably in amounts of from 0 to 10, morepreferably from 0 to 3, particularly preferably from 0 to 1.5 and mostpreferably from 0 to 0.9, parts by weight per 100 parts by weight of thetotal amount of components a) and b). If component d) is present in theinventive formulation, it is present in amounts of >0, preferably >0.01,part by weight, preferably up to a maximum of 1 part by weight, per 100parts by weight of the total amount of components a) and b).

Component f) is added preferably in amounts of from 0 to 710, morepreferably from 0 to 300 and particularly preferably from 0 to 100,parts by weight per 100 parts by weight of the total amount ofcomponents a) and b). If component f) is present in the inventiveformulation, it is present in amounts of >0 part by weight,preferably >5 parts by weight, per 100 parts by weight of the totalamount of components a) and b).

Component g) is added preferably in amounts of from 0 to 710, morepreferably from 0 to 300 and particularly preferably from 0 to 100,parts by weight per 100 parts by weight of the total amount ofcomponents a) and b). If component g) is present in the inventiveformulation, it is present in amounts of >0 part by weight,preferably >5 parts by weight, per 100 parts by weight of the totalamount of components a) and b).

Component e), i.e. component f) and/or g), is added preferably inamounts of from 0 to 1420, more preferably from 0 to 600 andparticularly preferably from 0 to 200, parts by weight per 100 parts byweight of the total amount of components a) and b).

Component a) of the inventive formulation is a nitrogen-freepolysiloxane compound. It preferably comprises straight-chain, cyclic,branched or partially crosslinked polydiorganosiloxanes in which theorgano group is preferably selected from: C₁ to C₆ alkyl groups,polyalkyleneoxy groups whose end groups may be hydroxyl, ether or estergroups and which are preferably bonded to the silicon via alkylenegroups, and aryl groups, and where the polydiorganosiloxanes maylikewise optionally have functional groups, especially hydroxyl andalkoxy groups, on the silicon, with the exclusion of nitrogen-containinggroups. The organo groups are more preferably selected from methyl,ethyl, butyl, phenyl, poly(ethyleneoxy) andcopoly(ethyleneoxy)(propyleneoxy) groups. Greatest preference is givento polydialkylsiloxanes, especially polydimethylsiloxanes. Thenitrogen-free, functionalized or unfunctionalized polysiloxane compoundsas per component a), especially the polydimethylsiloxanes, appropriatelyhave a viscosity in the range from 100 to 50 000 000 mPa·s, preferablyfrom 10 000 to 20 000 000 mPa·s, more preferably from 10 000 to 10 000000 mPa·s, more preferably between 100 000 and 10 000 000 mPa·s, such asbetween 100 000 and 1 000 000 mPa·s and between 1 000 000 and 10 000 000mPa·s, at 25° C. and a shear rate gradient of D=1 s⁻¹.

The polysiloxane compounds as per component a) which have functionalgroups are, for example, α,ω-dihydroxy-terminated polydimethylsiloxanes.

The amount of component a), based on the total amount of theformulation, is preferably in the range from 0.3% by weight to 99% byweight, preferably from 1.2% by weight to 90% by weight, more preferablyfrom 1.8% by weight to 80% by weight and most preferably from 5% byweight to 70% by weight.

Examples of the polysiloxane compounds as per the definition ofcomponent a) are described, for example, in “Silicone Surfactants”, ed.:R. M. Hill, Surfactant Science Series, Vol. 86, Marcel Dekker, Inc.,1999.

Preferred polysiloxane compounds as per the definition of component a)include, for example, silicone polymers of the formulae (II) to (III):

and mixtures thereof,

-   in which R²⁴ is in each case independently selected from the group    consisting of: hydroxyl groups, linear, branched or cyclic alkyl    groups having from 1 to 22 carbon atoms, linear, branched or cyclic    alkenyl groups having from 2 to 22 carbon atoms, linear, branched or    cyclic alkoxy groups having from 1 to 8 carbon atoms, phenyl;    alkylaryl groups having from 7 to 20 carbon atoms; arylalkyl groups    having from 7 to 20 carbon atoms, a poly(ethylene oxide/propylene    oxide) copolymer group of the general formula (IV):    —R²⁵—O(C₂H₄O)_(c)(C₃H₆O)_(d)-R²⁶  (IV)

in which R²⁵ is a straight-chain, branched or cyclic alkanediyl groupwhich has from 3 to 22 carbon atoms and may optionally be interrupted byone or more oxygen atoms, and R²⁶ is independently selected from thegroup consisting of hydrogen, alkyl having from 1 to 16 carbon atoms andan acetyl group, where the index a is appropriately selected in such away that the viscosity of the nitrogen-free silicone polymer of theformula (II), for the derivatives of this class which are liquid at 25°C., is between 1 to 20 mPa·s and the index b is appropriately selectedin such a way that the viscosity of the nitrogen-free silicone polymerof the formula (III), for the derivatives of this class which are liquidat 25° C., is between 1 to 50 000 000 mPa·s. The index “a” or theaverage degree of polymerization as M_(n) is preferably from 3 to 6 andthe index “b” or the average degree of polymerization as M_(n) ispreferably from 300 to 5000; where the viscosity values given in thepresent application are measured at a temperature of 25° C. and a shearrate gradient of D=1 s⁻¹; and where c+d=from 1 to 10 000 and c=from 1 to10 000 and d=from 0 to 100, and the ethyleneoxy and propyleneoxy groupsare arranged randomly or in block form, preferably randomly.

Examples of the nitrogen-free silicone polymers of the formula (III) arethe Silwet® compounds from OSi Specialties of Crompton, Middlebury,Conn., USA, or Tegostab from Goldschmidt, Essen, or the SF PU foamstabilizer types from GE Bayer Silicones GmbH and Co KG, Leverkusen.

Further examples of the compounds of the formulae (II) and (III) arepolydimethylsiloxane oils, for example from GE Bayer Silicones GmbH andCo. KG, of the Baysilone M series, or silicone oils of the 200 seriesfrom Dow Corning.

The preferred amount of component a) in the formulation, based on thetotal amount of the formulation, is from 5 to 99% by weight, preferablyfrom 10 to 80% by weight, more preferably from 10 to 40% by weight.

The component b) used in accordance with the invention is at least onepolyamino- and/or polyammonium-polysiloxane compound b1) and/or at leastone amino- and/or ammonium-polysiloxane compound b2). The polyamino-and/or poly-ammonium-polysiloxane compound b1) is a copolymer compoundwhich has amino and/or ammonium repeat units and polysiloxane repeatunits in the polymer main chain. The amino units contain secondaryand/or tertiary nitrogen atoms (2 or 3 organic radicals on the unchargednitrogen atom). The ammonium units contain secondary, tertiary and/orquaternary, positively charged nitrogen atoms (2, 3 or 4 organicradicals on the nitrogen). The amino and/or ammonium repeat units mayalso serve heterocyclic radicals bonded into the polymer chain via twonitrogen atoms.

In contrast, component b2) comprises polysiloxane compounds whichcontain amino and/or ammonium groups in the pendent groups of thepolysiloxane main chain. In other words, the amino and/or ammoniumgroups are not present in the main chain composed of polysiloxane repeatunits.

The difference can be illustrated as follows:

-   polyamino- and/or polyammonium-polysiloxane compound b1):-   -Amino/Ammonium    Polyorganosiloxane-Amino/Ammonium    _(i)Polyorgagosioxane-amino- and/or ammonium-polysiloxane compound    b2):

In the inventive formulation, components b1) and b2) serve principallyas a substantivity-imparting component.

In the inventive formulation, components b1) and b2) may be presentalone or together. In a preferred embodiment, component b1) is, however,present alone in the inventive formulation, without component b2). In alikewise preferred embodiment, both component b1) and component b2) arepresent together.

Components b1) or b2) may be present together in any ratios relative toone another.

The polyamino- and/or polyammonium-polysiloxane compound b1) preferablycomprises polysiloxane compounds which contain at least one unit of theformula (I):-[Q-V]—  (I)in which Q is selected from the group consisting of:

-   -   —NR—,    -   —NR⁺R₂—    -   a saturated or unsaturated diamino-functional heterocycle of the        formulae:        an aromatic diamino-functional heterocycle of the formula:        a trivalent radical of the formula:        a trivalent radical of the formula:        a tetravalent radical of the formula        in which R is in each case hydrogen or a monovalent organic        radical,

-   where Q is not bonded to a carbonyl carbon atom,

-   V is at least one constituent which is selected from the group    consisting of V¹, V² and V³, where

-   V² is selected from divalent, straight-chain, cyclic or branched,    saturated, unsaturated or aromatic hydrocarbon radicals which have    up to 1000 carbon atoms (not counting the carbon atoms of the    polysiloxane radical Z² defined below) and may optionally contain    one or more groups selected from    —O—, —CONH—,    -   —CONR²—, in which R² is hydrogen, a monovalent, straight-chain,        cyclic or branched, saturated, unsaturated or aromatic        hydrocarbon radical which has up to 100 carbon atoms, may        contain one or more groups selected from —O—, —NH—, —C(O)— and        —C(S)—, and may optionally be substituted by one or more        substituents selected from the group consisting of a hydroxyl        group, an optionally substituted heterocyclic group preferably        containing one or more nitrogen atoms, amino, alkylamino,        dialkylamino, ammonium, polyether radicals and polyether ester        radicals, where, when a plurality of —CONR² groups is present,        they may be the same or different,        —C(O)— and —C(S)—,        the V² radical may optionally be substituted by one or more        hydroxyl groups, and

-   the V² radical contains at least one -Z²- group of the formula    in which

-   R¹ may be the same or different and is selected from the group    consisting of: C₁ to C₂₂ alkyl, fluoro(C₁-C₁₀)alkyl and C₆-C₁₀ aryl,    and n₁=from 20 to 1000,

-   V¹ is selected from divalent, straight-chain, cyclic or branched,    saturated, unsaturated or aromatic hydrocarbon radicals which have    up to 1000 carbon atoms and may optionally contain one or more    groups selected from    —O—, —CONH—,    -   —CONR²—, in which R² is as defined above, where the R² groups in        the V¹ and V² groups may be the same or different,    -   —C(O)—, —C(S)— and -Z¹-, where -Z¹- is a group of the formula    -   in which    -   R¹ is as defined above, where the R¹ groups in the V¹ and V²        groups may be the same or different, and    -   n₂=from 0 to 19,

-   and the V¹ radical may optionally be substituted by one or more    hydroxyl groups, and

-   V³ is a trivalent or higher-valency, straight-chain, cyclic or    branched, saturated, unsaturated or aromatic hydrocarbon radical    which has up to 1000 carbon atoms, may optionally contain one or    more groups selected from    -   —O—, —CONH—, —CONR²—, in which R² is as defined above, —C(O)—,        —C(S)—, -Z¹- which is as defined above, -Z²- which is as defined        above and Z³, where Z³ is a trivalent or higher-valency        organopolysiloxane unit, and

-   may optionally be substituted by one or more hydroxyl groups,

-   where, in said polysiloxane compound, in each case one or more V¹    groups, one or more V² groups and/or one or more V³ groups may be    present, with the proviso    -   that said polysiloxane compound contains at least one V¹, V² or        V³ group which contains at least one -Z¹-, -Z²- or Z³ group, and    -   that the tri- and tetravalent Q radicals either serve to branch        the main chain formed from Q and V, so that the valencies which        do not serve for bonding in the main chain bear further branches        formed from -[Q-V]— units, or the tri- and tetravalent Q        radicals are saturated with V³ radicals within a linear main        chain without formation of a branch,

-   and wherein the positive charges resulting from ammonium groups are    neutralized by organic or inorganic acid anions, and acid addition    salts thereof.    The polysiloxane compounds which contain at least one unit of the    formula (I) are terminated by monofunctional -Q-R and/or —V—R    groups, i.e., for example, by amino groups. These arise by    saturation of one of the two binding points of Q or V by a    monovalent R group or hydrogen, which is as defined above, and are    also referred to below as V^(st) or Q^(st). Instead of V^(st), other    unconverted reactive groups such as epoxy or haloalkyl groups may    also be present.

In the context of the invention, the polysiloxane compounds whichcontain at least one unit of the formula (I) are also intended toinclude the case where only one -[Q-V]— unit is present, so thatcompounds of the formula R—V-[Q-V]—R or R-[Q-V]-Q-R, where R may also bereplaced by H, are also included.

Suitable polyamino- and/or polyammonium-polysiloxane compounds b1) aredescribed, for example, in WO 02/10257, WO 02/10259, DE-A 100 36 522,DE-A 100 36 532, DE-A 100 36 533 and the unpublished DE application 10212 470.1. In addition, the compounds may also be according to U.S. Pat.No. 6,240,929.

The polysiloxane compounds which contain at least one unit of theformula (I) are, for example, linear polysiloxane copolymers of thegeneral formula (I′):-[Q-V]—  (I′)in which Q is as defined above,

-   V is at least one V¹ group and at least one V² group,-   where V¹ and V² are each as defined above. In addition, V may also    be trivalent or higher-valency, particularly trivalent, V³ radicals.    In this case, tri- or tetravalent Q units, as defined above, are    also present, and the trivalent or higher-valency V³ radicals and    the tri- or tetravalent Q units are saturated exclusively by one    another within the linear main chain to form cyclic structures, as    illustrated in more detail below. However, this case is less    preferred.

In a preferred embodiment of the polyamino- and/orpolyammonium-polysiloxane copolymers b1) of the formulae (I) or (I′), Qis therefore selected from the group consisting of:—NR—,—NR⁺R2-

a saturated or unsaturated diamino-functional heterocycle of theformulae:

an aromatic diamino-functional heterocycle of the formula:

in which R is as defined above, and V is selected from V¹ and V².

In the general formulae (I) and (I′), the molar ratio of the V¹ and V²groups in the polysiloxane compounds V²/V¹ may in principle assume anyvalue. The invention thus also includes the case in which thepolysiloxane compound of the formulae (I) or (I′) contains only V²units, i.e. the polysiloxane compound has the formula -[Q-V²]—. Theinvention also embraces the case in which the polysiloxane compoundcontains only V¹ units. However, in this case, the V¹ units have tocontain Z¹-siloxane units.

In a preferred embodiment of the invention, however, the polysiloxanecompound of the formulae (I) or (I′) contains both V² and V¹ units.

In a further preferred embodiment of the present invention, the molarratio of the V¹ and V² groups in the polysiloxane compounds of thegeneral formulae (I) and (I′) is:V²/V¹=1.Such linear amine and tetraorganoammonium compounds have been described,for example, in WO 02/10257, WO 02/10259, EP 282720 or U.S. Pat. No.5,981,681. Particular preference is given to the polysiloxanes of WO02/10259 and WO 02/10257, and reference is made here explicitly to thepolysiloxane polymers defined in claims 1 which form part of thedisclosure content of the present application.

In a further embodiment of the linear polysiloxane compounds of theformula (I) or (I′), V²/V¹ does not equal 1; preferably, V²/V¹ is <1,more preferably <0.9; even more preferably, V²/V¹ fulfills therelationship0.0005<V²/V¹<0.5,more preferably0.0005<V²/V¹<0.3.

The R group is preferably selected from the R² groups.

In a preferred embodiment of the invention, Q is a divalent radical andis selected in the formulae (I) or (I′) from the group consisting of:—NR—,—NR⁺R2-a quaternized imidazole unit of the structure

a quaternized pyrazole unit of the structure

a diquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a diquaternized unit of the structure

a monoquaternized unit of the structure

a monoquaternized unit of the structure

a diquaternized unit of the structure

a monoquaternized unit of the structure

and a monoquaternized unit of the structure

in which

-   t is from 2 to 10,-   R is as defined above, preferably R², R² is as defined above, and    the definition of R² and the definition of the above R² group may be    the same or different,-   R³ has the definition of R², where R² and R³ may be the same or    different, or-   R² and R³ together with the positively charged nitrogen atom form a    five- to seven-membered heterocycle which may optionally    additionally have one or more nitrogen, oxygen and/or sulfur atoms,-   R⁵, R⁶, R⁷ may be the same or different and are selected from the    group consisting of: H, halogen, hydroxyl group, nitro group, cyano    group, thiol group, carboxyl group, alkyl group, monohydroxyalkyl    group, polyhydroxyalkyl group, thioalkyl group, cyanoalkyl group,    alkoxy group, acyl group, acetyloxy group, cycloalkyl group, aryl    group, alkylaryl group, and groups of the —NHR^(w) type in which    R^(w) is H, alkyl group, monohydroxyalkyl group, polyhydroxyalkyl    group, acetyl group, ureido group, and in each case two of the    adjacent R⁵, R⁶ and R⁷ radicals with the carbon atoms binding them    to the heterocycles may form aromatic five- to seven-membered rings,    and-   R⁸ has the definition of R², where R⁸ and R² may be the same or    different.

In the case that Q is a trivalent radical of the formulae

or a tetravalent radical

these radicals in the linear copolymers of the formula (I′), asmentioned above, do not serve to branch the polysiloxane copolymers, butrather these radicals are bonded exclusively to especially trivalent V³radicals to form cyclic structures which are part of the linear mainchain, for example a structural element of the formula:

In a preferred embodiment of the polysiloxane compounds of the formula(I) or (I′) as component b1), V² is a group of the formula—V^(2*)-Z²-V^(2*)—in which Z² is as defined above and V^(2*) is a divalent, straight-chaincyclic or branched, saturated, unsaturated or aromatic hydrocarbonradical which has up to 40 carbon atoms and may optionally contain oneor more groups selected from —O—, —CONH—, —CONR²— in which R² is asdefined above, —C(O)— and —C(S)—, and the V^(2*) radical may optionallybe substituted by one more hydroxyl groups.

In the aforementioned embodiment, the inventive linear polysiloxanecopolymer may have the following repeat units:[V^(2*)-Z²-V^(2*)-Q]-, preferably together with —[V¹-Q]-.

The molar ratio of the repeat units [V^(2*)-Z²-V^(2*)-Q]- to —[V¹-Q]-,i.e. the V²/V¹ ratio, may, as mentioned above, be 1, but is, in oneembodiment, preferably unequal to 1, more preferably <0.9, even morepreferably <0.8, even more preferably <0.3. In the cases where V²/V¹<1,the linear polysiloxane copolymers -[Q-V]— mentioned necessarily containblocks which contain more than one —[V¹-Q]- unit joined together.

As is explained in detail below in connection with the process forpreparing the above-described linear polysiloxane- copolymers, theblocklike sequences which have more than one —[V¹-Q]- unit joinedtogether may, depending on the preparation method, be bonded regularlywith the V²-Q units or irregularly with the V²-Q units.

This means the following:

-   In the case of regular bonding, in which, for example, a prepolymer    corresponding to the -[Q-[V1-Q]_(x)- group is reacted with monomer    units corresponding to V² in a molar ratio of 1:1, the linear    polysiloxane copolymers can be represented as follows:    —{V²-Q-[V¹-Q]_(x)-}-.    In this formula, x may be from 2 to 2000 and is the median of the    distribution. The linear polysiloxane copolymers represented by the    formula —{V²-Q-[V¹-Q]_(x)-}- are characterized in that they have    substantially no —V²-Q- units joined to one another, or, in other    words, two —V²-Q- units are always interrupted by at least one    —V¹-Q- unit.

In the case of irregular bonding, in which, for example, monomerscorresponding to Q units are reacted with monomer units corresponding toV¹ and monomer units corresponding to V² in a ratio of Q/(V¹+V²), where,for example, V²/V¹<1, preferably <0.5, of 1:1, the linear polysiloxanecopolymers can be represented as follows:-Q-(V¹, V²)—in which V the V²/V¹ ratio is <1 or <0.5. In this formula, the V¹ and V²groups are distributed randomly over the copolymer chain. In contrast tothe linear polysiloxane copolymers prepared by the regular bonding, thiscopolymer may also have adjacent -Q-V²— units.

In a preferred embodiment of the polysiloxane compound of the formula(I) or (I′) used in accordance with the invention as component b1), theV¹ group is selected from divalent, straight-chain, cyclic or branched,saturated, unsaturated or aromatic hydrocarbon radicals which have up to600, preferably up to 400, carbon atoms and may optionally contain oneor more groups selected from —O—, —CONH—, —CONR²— in which R² is asdefined above, —C(O)—, —C(S)— and -Z¹-, where -Z¹- is a group of theformula

in which

-   R¹ is C₁-C₁₈ alkyl which may optionally be substituted by one or    more fluorine atoms or is phenyl, and n₂ is as defined above.

In a further preferred embodiment of the polysiloxane compounds of theformula (I) or (I′) as component b1), the Q group is selected from:

a quaternized imidazole unit of the structure,

a quaternized pyrazole unit of the structure

a diquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a monoquaternized unit of the structure

in which R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are each as defined above.

In a further preferred embodiment of the linear polysiloxane compoundsof the formula (I′) as component b1) of the present invention, the molarratio V²/V¹ fulfills the relationship0.0005<V²/V¹<0.5(=2<V¹/V²<2000)more preferably the relationship0.005<V²/V¹<0.4(=2.5<V¹/V²<200)even more preferably the relationship0.01<V²/V¹<0.3(=3.3<V¹/V²<100).In the formulae (I) and (I′), preferably:

-   R¹=C₁ to C₁₈ alkyl, in particular methyl, ethyl, trifluoropropyl and    phenyl,-   n₁=from 20 to 400, more preferably from 20 to 300, especially from    20 to 200. In a further preferred embodiment, n, is between 20 and    50 or between 80 and 200. The number n₁ is the average degree of    polymerization from M_(n) of the diorganosiloxy units in the Z²    group.-   n₂=from 0 to 15, more preferably from 0 to 10, especially from 0 to    5, more especially 0. The number n₂ is the average degree of    polymerization from M_(n) of the diorganosiloxy units in the Z¹    group.

V^(2*)=a divalent straight-chain, cyclic or branched, saturated,unsaturated C₃ to C₁₆ hydrocarbon radical or aromatic C₈ to C₂₀hydrocarbon radical which may optionally contain one or more groupsselected from —O—, —CONH—, —CONR²—, —C(O)—, —C(S)— and may besubstituted by one or more OH groups, where R² is as defined above.

a quaternized imidazole unit of the structure

a diquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a monoquaternized unit of the structure

in which R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are each as defined above.More preferably,

-   V^(2*) is a divalent straight-chain, cyclic or branched, saturated,    unsaturated or aromatic hydrocarbon radical which has up to 16    carbon atoms, may be substituted by one or more groups selected from    —O—, —CONH—, —CONR²— in which R² is as defined above, —C(O)—, —C(S)—    and may be substituted by one or more hydroxyl groups. Even more    preferably, —V^(2*)— is selected from groups of the formulae:    R² is preferably: H,    where-   R⁴=straight-chain, cyclic or branched C₁ to C₁₈ hydrocarbon radical    which may be substituted by one or more groups selected from —O—,    —NH—, —C(O)— and —C(S)— and may be substituted by one or more OH    groups, especially unsubstituted C₅ to C₁₇ hydrocarbon radicals    which derive from the corresponding fatty acids or else hydroxylated    C₃ to C₁₇ radicals which can be traced back to hydroxylated    carboxylic acids, especially saccharide carboxylic acids, and quite    especially

Moreover, R² is preferably:

in which t, R⁵ and R⁸ are each as defined above,

in which t, R⁵ to R⁷ are each as defined above,

in which t, R², R³ and R⁸ are each as defined above.

-   V¹ is preferably    -   —R⁹—, in which R⁹ is a divalent, saturated or mono- or        polyunsaturated, straight-chain or branched hydrocarbon radical        having from two to 25 carbon atoms,    -   —(CH₂)_(u)C(O)O—[(CH₂CH₂O)_(q)-(CH₂CH(CH₃),O_(r)]-C(O)(CH₂)_(u)    -   —(CH₂)_(u)C(O)O—R⁹—O—C(O)(CH₂)_(u)- in which R⁹ is as defined        above,    -   —(CH₂)_(u)-R¹⁰—(CH₂)_(u)- in which R¹⁰ is an aromatic group,    -   —[CH₂CH₂O]_(q)-[CH₂CH(CH₃)O]_(r)-CH₂CH₂—,    -   —CH(CH₃)CH₂O[CH₂CH₂O]_(q)-[CH₂CH(CH₃)O]_(r)-CH₂CH(CH₃)—    -   —CH₂CH(OH)CH₂—,    -   —CH₂CH(OH)(CH₂)₂CH(OH)CH₂—,    -   —CH₂CH(OH)CH₂OCH₂CH(OH)CH₂OCH₂CH(OH)CH₂— and    -   —CH₂CH(OH)CH₂O—[CH₂CH₂O]_(q)-[CH₂CH(CH₃)O]_(r)-CH₂CH(OH)CH₂—        in which-   u is from 1 to 3,-   q and r are each from 0 to 200, preferably from 0 to 100, more    preferably from 0 to 70 and particularly preferably from 0 to 40,    and-   q+r>0.

Preferred variants of V¹ are structures of the formula:

-   —CH₂C(O)O—[CH₂CH₂O]_(q)-[CH₂CH(CH₃)O]_(r)-C(O)CH₂—,-   —CH₂CH₂C(O)O—[CH₂CH₂O]_(q)-[CH₂CH(CH₃)O]_(r)-C(O)CH₂CH₂—,-   —CH₂CH₂CH₂C(O)O—[CH₂CH₂O]_(q)-[CH₂CH(CH₃)O]_(r)-C(O)CH₂CH₂CH₂—,    esterified alkylene, alkenylene, alkynylene units, especially of the    structures-   —CH₂C(O)O—[CH₂]_(o)-OC(O)CH₂—,-   —CH₂CH₂C(O)O—[CH₂]_(o)-OC(O)CH₂CH₂—,-   —CH₂CH₂CH₂C(O)O—[CH₂]_(o)-OC(O)CH₂CH₂CH₂—-   —CH₂C(O)O—CH₂C≡CCH₂—OC(O)CH₂—,-   —CH₂CH₂C(O)O—CH₂C≡CCH₂—OC(O)CH₂CH₂—,-   —CH₂CH₂CH₂C(O)O—CH₂C≡CCH₂—OC(O)CH₂CH₂CH₂—,-   —CH₂C(O)O—CH₂CH═CHCH₂—OC(O)CH₂—,-   —CH₂CH₂C(O)O—CH₂CH═CHCH₂—OC(O)CH₂CH₂—,-   —CH₂CH₂CH₂C(O)O—CH₂CH═CHCH₂—OC(O)CH₂CH₂CH₂—,    alkylene, alkenylene, alkynylene and aryl units, especially of the    structures:-   —[CH₂]o--   where o=from 2 to 6,-   —CH₂C≡CCH₂—, —CH₂CH═CHCH₂—, —CH(CH₃)CH₂CH₂—,    polyalkylene oxide units, especially of the structures-   —[CH₂CH₂O]_(q)-[CH₂CH(CH₃)O]_(r)-CH₂CH₂—,-   —CH(CH₃)CH₂O[CH₂CH₂O]_(q)-[CH₂CH(CH₃)O]_(r)-CH₂CH(CH₃)—    with-   mono-, di- or polyhydroxy-functional units, especially of the    structures-   —CH₂CH(OH)CH₂—, —CH₂CH(OH)(CH₂)₂CH(OH)CH₂—,-   —CH₂CH(OH)CH₂OCH₂CH(OH)CH₂OCH₂CH(OH)CH₂—,-   —CH₂CH(OH)CH₂O—[CH₂CH₂O]_(q)-[CH₂CH(CH₃)O_(r)-CH₂CH(OH)CH₂—    where-   q=from 0 to 200,-   r=from 0 to 200.-   Preferably, q=from 1 to 50, in particular from 2 to 50, especially    from 1 to 20, very especially from 1 to 10, and also 1 or 2, r=from    0 to 100, in particular from 0 to 50, especially from 0 to 20, very    especially from 0 to 10, and also 0 or 1 or 2.    The linear polysiloxanes of the formulae (I) or (I′) may be    prepared, for example, by a process in which-   a) at least one amine compound selected from a diamine compound    and/or a primary or secondary monoamine compound is reacted with at    least two difunctional organic compounds capable of reaction with    the amino functions of the amine compound, the molar ratio of the    organic compounds being selected in such a way that the desired    V²/V¹ ratio is obtained,-   b) at least two mol of an amine compound selected from a diamine    compound and/or a primary or secondary monoamine compound is reacted    with one mole of a difunctional organic compound capable of reaction    with the amino functions of the amine compound to form a diamine    compound (monomer) which is subsequently reacted with at least one    amine compound selected from a diamine compound and/or a primary or    secondary monoamine compound and at least one further difunctional    organic compound capable of reaction with the amino function of the    amine compounds,-   c) an amine compound selected from a diamine compound and/or a    primary or secondary monoamine compound is reacted with a    difunctional organic compound capable of reaction with the amino    functions of the amine compounds to form a diamine compound    (amino-terminated oligomer) which is subsequently reacted with at    least one difunctional organic compound capable of reaction with the    amino functions of the diamine compounds,-   d) an amine compound selected from a diamine compound and/or a    primary or secondary monoamine compound is reacted with a    difunctional organic compound capable of reaction with the amino    functions of the amine compound to form a difunctional compound    capable of reaction with amino functions (difunctional oligomer)    which is subsequently reacted with at least one amine compound    selected from a diamine compound and/or a primary or secondary    monoamine compound and at least one further compound capable of    reaction with amino functions,    where monofunctional, preferably tertiary, monoamines or suitable    monoamines incapable of chain propagation and/or monofunctional    compounds capable of reaction with amino functions may optionally be    added as chain terminators, and the stoichiometry of the amino    functions and of the functional groups capable of reaction with    amino functions in the last stage of the reaction is always about    1:1, and where any amino functions present may be protonated or    quaternized.    Variant a), in which at least one diamine compound selected from a    diamine compound and/or a primary or secondary monoamine compound is    reacted with at least two difunctional organic compounds capable of    reaction with the amino functions of the amine compound, the molar    ratio of the organic compounds being selected such that the desired    V²/V¹ ratio, for example <0.5, is fulfillled, can thus be    represented schematically, for example, as follows:    —[N—N]—+—[V¹]—+—[V²]—→[Q-(V¹, V²)]— or    —N]—+—[V¹]—+—[V²]—→-[Q-(V¹, V²)—    where —[N—N]—, can include an acyclic diamine corresponding to the    definition of Q or a V¹-containing diamine —[N—V¹—N]— or a    V²-containing diamine —[N—V²—N]—, in particular    —[N—V^(2*)-Z²-V^(2*)—N]—, the latter giving rise in each case to two    Q units and one V unit or two V² units, and -[v¹]— and —[V²]— are    intended to represent the monomers corresponding to the repeat units    V¹ and V², and —[N]— is a primary or secondary monoamine suitable    for chain propagation.

From the —[N—N]— and/or —[N]— units, at least one relatively highlyalkylated amine or a quaternary ammonium unit Q is formed, and secondaryor tertiary amino functions formed in the polymerization may optionallybe protonated or quaternized in a separate step after thepolymerization. Preference is given to the formation of quaternaryammonium units.

Preferred examples of —[N—N]— are as described in more detail below:piperazine and imidazole; preferred diamine units —[N—V¹—N]— include,for example: polymethylenediamines such astetramethylhexamethylenediamine, α,ω-diamino-terminated polyethers, forexample Jeffamines, etc.

Preferred diamine units —[N—V^(2*)-Z²-V^(2*)—N]— include, for example,reaction products of α,ω-dihydropolydialkylsiloxanes with allylamines.

Preferred examples of —[N]— are as described in more detail below, forexample dimethylamine.

The use of diamines —[N—N]— is preferred in principle.

Preferred —[V¹]— monomers include, for example, epichlorohydrin,bischloroalkyl esters, bisepoxides or bisacrylates. It is also possiblewith preference to use mixtures of the —[V¹]— monomers mentioned, forexample mixtures of epichlorohydrin, bischloroalkyl esters orbisepoxides.

Preferred —[V²]— monomers are monomers of the formula—[V^(2*)-Z²-V^(2*)] in which Z² is as defined above and —[V^(2*)] is afunctionalized group corresponding to the V^(2*) repeat unit. Preferred—[V^(2*)] monomers for the formation of the V² repeat units are inparticular α,ω-diepoxy-terminated polydialkylsiloxanes.

Variant b) can be carried out either with diamines —[N—N]— or suitablemonoamines —[N]— and can be represented schematically, for example, asfollows:

Variant b1)

-   Step 1): 2-[N—N]—+—[V²]— or —[V¹]—→—[N—N—V¹—N—N]— or-   —[N—N—V²—N—N]—-   Step 2.1): —[N—N—V²—N—N]—→—[V¹]—+—[N—N]—→,-   Step 2.2): —[N—N—V¹—N—N]—+—[V²]—+—[N—N]—→,-   where the stoichiometry V²/V¹ is established as desired.    With regard to the —[N—N]—, —[V¹]— and —[V²]— monomer units used    with preference, the same applies as was stated for step a).    Variant b2)-   Step 1): 2-[N]]—+—[V²]— or —[V¹]—→—[N—V¹—N]— or —[N—V²—N]—-   Step 2.1): —[N—V²—N]—+—[V¹]—+—[N]—→,-   Step 2.2): —[N—V¹—N]—+—[V²]—+—[N]—→,-   where this variant, as mentioned above, can be carried out only with    primary or secondary monoamines and where, with regard to the —[N]—,    —[V¹]— and —[V²]— monomer units used with preference, the same    applies as was stated for step a).    Variant c) can be represented schematically, for example, as    follows:    Variant c1)-   Step 1): —[N—N]—+—[V¹]—→—[N—N—(V¹—N—N)_(x)]--   Step 2): —[N—N—(V¹—N—N)_(x)]-+—[V²]—→-   where, with regard to the —[N—N]—, —[V¹]— and —[V²]— monomer units    used with preference, the same applies as was stated for step a).    Variant c2)-   Step 1): —[N]—+—[V¹]—→—[N—(V¹—N)_(x)]--   Step 2): —[N—(V¹—N)_(x)]-+—[V²]—→-   where, with regard to the —[N]—, —[V¹]— and —[V²]— monomer units    used with preference, the same applies as was stated for step a).    Variant d) can be represented schematically, for example, as    follows:    Variant d1)-   Step 1): —[V¹]—+—[N—N]—→[V¹—(N—N—V¹)_(x)]--   Step 2): —[V¹—(N—N—V¹)_(x)]-+—[V²]—+—[N]— or —[N—N]—→-   where, with regard to the —[N—N]—, —[V¹]— and —[V²]— monomer units    used with preference, the same applies as was stated for step a).    Variant d2)-   Step 1): —[V¹]—+—[N]—→—[V¹—(N—V¹)_(x)]--   Step 2: —[V¹—(N—V¹)_(x)]-+—[V²]—+—[V²]—+—[N]— or —[N—N]→-   where, with regard to the —[N—N]—, —[V¹]— and —[V²]—monomer units    used with preference, the same applies as was stated for step a).    For all variants represented schematically above, it is also    possible to use mixtures of monoamines —[N]— and diamines —[N—N]—.    Particular preference is given to selecting the functional groups of    the difunctional compounds capable of reaction with amino functions    from the group consisting of epoxy groups and haloalkyl groups.    A preferred starting point for the syntheses of the polysiloxane    copolymers of the formulae (I) and (I′) used in accordance with the    invention is α,ω Si—H functionalized siloxanes of the general    structure    where R¹ is as defined above and n, depending on the desired V¹ or    V² repeat units, is n₁ or n₂ which are as defined above. When they    are not commercially available, these siloxanes may be prepared by    known processes, for example by equilibration (Silicone, Chemie und    Technologie [Silicones, chemistry and technology], Vulkan-Verlag,    Essen 1989, p. 82-84).    The precursors of the structural elements V^(2*) and Q may be    prepared, for example, by two routes.    On the one hand, it is possible first to bind unsaturated structures    bearing tertiary amino functions, for example    N,N-dimethylallylamine, by hydrosilylation directly to the siloxane    in α,ω arrangement. This process is common knowledge (B. Marciniec,    Comprehensive Handbook on Hydrosilylation, Pergamon Press, Oxford    1992, p. 122-124).    On the other hand, it is preferred initially to generate by    hydrosilylation reactive (α,ω-functionalized intermediates which can    subsequently be converted to α,ω)-ditertiary amino structures or    directly to the inventive quaternary ammonium structures. Suitable    starting materials for generating reactive intermediates are, for    example, halogenated alkenes or alkynes, especially allyl chloride,    allyl bromide, chloropropyne and chlorobutyne, unsaturated    halocarboxylic esters, especially allyl chloroformate, propargyl    chloroformate, allyl 3-chloropropionate and propargyl    3-chloropropionate and epoxy-functional alkenes, for example    vinylcyclohexene oxide and allyl glycidyl ether. The general    performance of hydrosilylations with representatives of the    substance groups mentioned is likewise known (B. Marciniec,    Comprehensive Handbook on Hydrosilylation, Pergamon Press, Oxford    1992, p. 116-121, 127-130, 134-137, 151-155).    In a subsequent step, the reactive intermediates may then be reacted    with compounds bearing secondary amino functions. Suitable    representatives are N,N-dialkylamines, for example dimethylamine,    diethylamine, dibutylamine, diethanolamine and N-methylglucamine,    cyclic secondary amines, for example morpholine and piperidine,    amino amides bearing secondary amino functions, for example the    reaction products of diethylenetriamine or dipropylenetriamine with    lactones such as γ-butyrolactone, δ-gluconolactone and    glucopyranosylarabonolactone (DE-A 43 18 536, examples 11a, 12a,    13a) or secondary-tertiary diamines, for example N-methylpiperazine.    It is especially preferred to utilize appropriate imidazole or    pyrazole derivatives, especially imidazole and pyrazole, for the    introduction of tertiary amino functions.    Suitable partners for the epoxide derivatives which are used with    preference in one embodiment are particularly the secondary-tertiary    diamines mentioned, and also imidazole and pyrazole. In this way, it    is possible to direct the alkylations to the nitrogen atoms bearing    hydrogen atoms regioselectively and without additional complexity.    To ensure a quantitative conversion of the reactive moieties to    tertiary amino structures, the amines are used in a ratio of 1≦Σ    secondary amino groups: reactive groups ≦10, preferably from 1 to 3,    especially from 1 to 2, very especially 1. Amine excesses have to be    removed in some cases.    The bonding of the above-described α,ω-ditertiary aminosiloxanes to    —[V¹]— monomer units corresponding to V¹ or a prepolymer unit    —[V¹-(Q-V¹)_(x)]- leads to the formation of further relatively    highly alkylated amino units or quaternary ammonium units and may in    turn be effected in two advantageous ways.    On the one hand, preference is given to separately generating a    strongly hydrophilic, polyquaternary, difunctional precondensate    —[V¹-(Q-V¹)_(x)]- which is combined at a suitable time with the    α,ω-ditertiary aminosiloxanes and reacts to give the polyamino or    polyquaternary siloxane copolymer.    The preparation of highly charged, difunctional prepolymers of    different chain length —[V¹-(Q-V¹)_(x)]- is described by way of    example in WO 99/14300 (examples 1 to 7, table 11). Depending on the    molar ratio of V¹ and the parent amine of Q, it is possible to    generate a prepolymer terminated either by amino groups or by other    reactive groups.    In the case of the binding of a prepolymer terminated by amino    groups —[N-(V¹—N)_(x)]- to the amine function of an α,ω-ditertiary    aminosiloxane structure, it is possible, for example, to use an    alkylating or quaternizing difunctional monomer —[V¹]— corresponding    to the repeat unit V¹, selected, for example, from bisepoxides,    epichlorohydrin, bishaloalkyl compounds. It need not be mentioned    here that different V¹ groups can result in the prepolymer and in    the linking group between prepolymer and α,ω-ditertiary    aminosiloxane structure.    In the case of a prepolymer terminated by reactive groups, such as    —[V¹-(Q-V¹)_(x)]-, direct bonding to the amine function of the    α,ω-ditertiary aminosiloxane structure may be effected without a    further linker, since an excess of the V¹-generating component has    already been used in the prepolymer synthesis.    Alternatively to the separate preparation of a precondensate    —[V¹-(Q-V¹)_(x)]-, highly charged blocks can be formed in parallel    to the incorporation into the copolymer. This means that the    α,ω-ditertiary aminosiloxane can be initially charged together with    the starting components for the formation of —[V¹-(Q-V¹)_(x)]-,    i.e., for example, —[V¹]— and mono- or diamines of the    abovementioned definition —[N]— and/or —[N—N]—, and reacted.    Finally, it is possible to meter the α,ω-ditertiary aminosiloxane    with a long-chain siloxane unit Z² or short-chain siloxane unit Z¹,    or the α,ω-difunctional siloxane —[N—V^(2*)-Z²-V^(2*)—N]— or    —[N—V¹—N]—, stepwise over a period of time into the initially    charged components for the formation of —[V¹-(Q-V¹)_(x)]-, or else,    conversely, to add these components stepwise to the α,ω-ditertiary    aminosiloxane or α,ω-difunctional siloxane.    A preceding preparation of prepolymers terminated by amino groups,    for example —[N-(V¹—N)_(x)]-, opens up the possibility of performing    the copolymer formation directly with suitable reactive    intermediates, for example epoxy derivatives.    It is likewise preferred to initially charge the reactive    intermediates and the starting components for the formation of    —[V¹-(Q-V¹)_(x)]- together and subsequently to react them.    Finally, it is possible to meter the reactive intermediates stepwise    over a period of time into the initially charged components for the    formation of —[V¹-(Q-V¹)_(x)]-, or else, conversely, to add these    components stepwise to the reactive intermediate.    Irrespective of the selection of the above-described reaction paths    and the closely related question of whether amino units terminate    the siloxane or else the prepolymer first, the overall stoichiometry    is selected such that the sum of the amino functions and of the    groups reactive with them is about 1:1.    In the context of the invention, it is possible to deviate from this    preferred overall stoichiometry. However, products are then obtained    which no longer have the envisaged length of the highly charged,    hydrophilic block —[V¹-(Q-V¹)_(x)]- and additionally leave behind an    excess of an unreacted starting component.    In addition to the overall stoichiometry, considered above, of the    reaction, the selection of the component(s) forming the V¹ repeat    unit is of great significance for the property profile of the    products.    Suitable difunctional parent monomers —[V¹]— of the V¹ repeat units    are, for example, the halocarboxylic esters of the polyalkylene    oxide diols. Preferred starting materials for their synthesis are    low molecular weight, oligomeric and polymeric alkylene oxides of    the general composition    HO[CH₂CH₂O]_(q)-[CH₂CH(CH₃)O]_(r)H    where q and r each have the definitions specified above, and the    units are random or blocklike. Preferred representatives with regard    to the alkylene oxide block are ethylene glycol, diethylene glycol,    triethylene glycol, tetraethylene glycol, the oligoethylene glycols    having molecular weights of from 200 to 10 000 g/mol, especially    from 300 to 800 g/mol, and also 1,2-propylene glycol, 1,3-propylene    glycol and dipropylene glycol.    The alkylene oxides are esterified in a manner known per se    (Organikum, Organisch-chemisches Grundpraktikum [Basic Organic    Chemistry Practicals], 17th edition, VEB Deutscher Verlag der    Wissenschaften, Berlin 1988, p. 402-408) by reaction with the C₂ to    C₄ halocarboxylic acids, their anhydrides or acid chlorides.    Preference is given to using the acid chlorides of chloroacetic acid    and 3-chloropropionic acid and to carrying out the reaction in the    absence of solvents.    In an analogous manner, it is possible to convert alkanediols,    alkenediols and alkyndiols to the corresponding reactive ester    derivatives. Examples of alcohols are 1,4-butanediol,    1,6-hexanediol, 1,4-but(-2-)enol and 1,4-but(-2-)ynol.    Alkylene, alkenylene, alkynylene and aryl units are introduced    preferably starting from the corresponding halides, especially    chlorides and bromides. Examples of representatives are    1,6-dichlorohexane, 1,4-dichlorobut(-2-)ene,    1,4-dichlorobut-(-2-)yne and 1,4-bis(chloromethyl)benzene.    Polyalkylene oxide units may likewise be introduced via the    α,ω-dihalogen compounds. These are obtainable from the oligomeric    and polymeric alkylene oxides of the general composition    HO[CH₂CH₂O]_(q)-[CH₂CH(CH₃)O]_(r)H    where q and r are each as defined above, for example by chlorination    of the hydroxyl groups with SOCl₂ (Organikum, Organisch-chemisches    Grundpraktikum, 17th edition, VEB Deutscher Verlag der    Wissenschaften, Berlin 1988, p. 189-190). Mono-, di- or    polyhydroxy-functional units as group V¹ may be introduced starting    from epoxide derivatives.    Commercial examples are 1-chloro-2,3-epoxypropane, glycerol    1,3-bisglycidyl ether and diethylene glycol diglycidyl ether and    neopentyl glycol diglycidyl ether.    When they are not commercially available, the desired diepoxides may    be synthesized, for example, by reaction of the corresponding diols    with 1-chloro-2,3-epoxypropane under alkaline conditions.    It lies within the scope of the invention to introduce siloxane    chains Z¹ into the structure of V¹. This gives rise, inter alia, to    the possibility of using siloxane chains of different length for the    formation of the overall molecule. It is a preferred variant to    incorporate into V¹ siloxane chains Z¹ of the chain length range    n₂=0 to 19, preferably from 0 to 15, more preferably from 0 to 10,    especially from 0 to 5, more especially 0. Suitable starting    materials for the incorporation are, for example, the corresponding    α,ω-diepoxides or α,ω-di(monohalocarboxylic acid) ester structures.    In the case of the reaction of epoxides with primary or secondary    amines, it should be noted that one mole of H⁺ has to be added per    mole of epoxide/tertiary amine for alkylations of tertiary amino    groups.    The selection of suitable amines as starting components for the    formation of Q in the —[V¹-(Q-V¹)_(x)]- repeat unit likewise    determines to a high degree the molecular structure. The use of    ditertiary amines (corresponding to —[N—N]—, for example    N,N,N′,N′-tetramethylethylenediamine,    N,N,N′,N′-tetramethyltetramethylenediamine,    N,N,N′,N′-tetramethylhexamethylenediamine, N,N′-dimethylpiperazine,    leads to products in which each nitrogen atom of the repeat unit is    quaternized.    The use of secondary-tertiary diamines, for example    N-methylpiperazine, opens up the route to repeat —[V¹-(Q-V¹)_(x)]-    units in which tertiary and quaternary amine and ammonium structures    are present in a ratio of 1:1. A partial or complete subsequent    quaternization of remaining tertiary amino structures constitutes a    preferred variant for the establishment of a desired high density of    the quaternary ammonium groups. The corresponding aromatic amines,    imidazole and pyrazole, lead to products having a delocalized    charge.    When primary-tertiary diamines, for example    N,N-dimethylpropylenediamine and 1-(3-aminopropyl)imidazole, are    used, especially in combination with diepoxides, it is possible to    form comb-like structures for which the degree of quaternization    during a final alkylation can be selected. In principle, the    alkylations may also be adjusted to degrees of quaternization of, on    average, less than one quaternary ammonium group per repeat    —[V¹-(Q-V¹)_(x)]- unit. However, preference is given to quaternizing    at least one nitrogen atom per repeat unit.    Starting from disecondary amines, for example piperazine,    N,N′-bis(2-hydroxyethyl)hexamethylenediamine,    N,N′-bis(2-hydroxypropyl)hexamethylenediamine, it is also possible    in principle to synthesize repeat —[V¹-(Q-V¹)_(x)]- units with an    average content of less than one quaternary ammonium group. In this    case, the disecondary amines initially afford polytertiary    amino-modified siloxane copolymers or else prepolymers which can    subsequently be quaternized partly or fully to —[V¹-(Q-V¹)_(x)]- in    a final reaction. However, it is preferred in this variant too to    quaternize at least one nitrogen atom per repeat unit.    Suitable quaternizing agents are the commonly known substance groups    such as alkyl halides, halocarboxylic esters, epoxide derivatives in    the presence of H⁺ and dialkyl sulfates, especially dimethyl    sulfate.    In a preferred embodiment, commercially unavailable disecondary    amines are prepared starting from the corresponding diprimary    amines, for example hexamethylenediamine, by alkylation with    epoxides, for example ethylene oxide, propylene oxide, isopropyl    glycidyl ether, utilizing the different reaction rates of primary    and secondary amines.    It has already been stated that the possibility exists within the    scope of the invention of introducing siloxane chains Z¹ into the    structure of V¹. Suitable starting materials named by way of example    have been the reactive intermediates α,ω-diepoxides and    α,ω-di(monohalocarboxylic acid) esters.    Useful anions A⁻ which neutralize the positive charges resulting    from the ammonium groups may preferably be the ions formed during    the quaternization, such as halide ions, especially chloride and    bromide, alkylsulfates, especially methosulfate, carboxylates,    especially acetate, propionate, octanoate, decanoate, dodecanoate,    tetradecanoate, hexadecanoate, octadecanoate, oleate, sulfonates,    especially toluenesulfonate. However, it is also possible to    introduce other anions by ion exchange. Mention should be made, for    example, of organic anions such as polyether carboxylates and    polyether sulfates.    The quaternization reactions are performed preferably in water,    polar organic solvents or mixtures of the two components mentioned.    Suitable solvents are, for example, alcohols, especially methanol,    ethanol, isopropanol and n-butanol, glycols such as ethylene glycol,    diethylene glycol, triethylene glycol, the methyl, ethyl and butyl    ethers of the glycols mentioned, 1,2-propylene glycol and    1,3-propylene glycol, ketones such as acetone and methyl ethyl    ketone, esters such as ethyl acetate, butyl acetate and 2-ethylhexyl    acetate, ethers such as tetrahydrofuran, and nitro compounds such as    nitromethane. The selection of the solvent depends substantially on    the solubility of the reaction partners, the desired reaction    temperature and any reactivity present which disrupts the reaction.    The reactions are carried out in the range from 20° C. to 130° C.,    preferably from 40° C. to 100° C.

In order to prevent the formation of gel-like linear polyorganosiloxanepolymers which are not fully soluble, an upper limit is appropriatelyplaced on the molar mass.

A limit in the molecular weight is brought about by the end-cappingresulting from the reaction between epoxides and any water or alcoholpresent in the reaction system, or alternatively by the additional useof tertiary amines such as trialkylamines or monofunctional compoundsreactive toward amino groups.

In other words, the polyorganosiloxane polymers may, in addition to theterminal groups which result by their nature from the reaction of themonomeric starting materials, also have from monofunctional chainterminators such as trialkylamines etc. and, for example, ammonium,amino, ether or hydroxyl end groups resulting therefrom. All cases ofend-capping are embraced by the aforementioned definition -Q-R and/or—V—R, where Q, V and R are each as defined above and R may be replacedby hydrogen.

The polysiloxanes of the general formula (I) used as component b1) inaccordance with the invention may also contain branch units V³. V³ is atrivalent or higher-valency, straight-chain, cyclic or branched,saturated, unsaturated or aromatic hydrocarbon radical which has up to1000 carbon atoms and may optionally contain one or more groups selectedfrom —O—, —CONH—, —CONR²— where R² is as defined above, —C(O)—, —C(S)—,-Z¹-, which is as defined above, -Z²- which is as defined above and Z³where Z³ is a trivalent or higher-valency organopolysiloxane unit. Thebranch unit V³ may be silicone-free. Examples thereof include:

where v+w≧0.The branch unit V³ may be a trivalent or high-valency organopolysiloxaneunit, for example:

in which R¹ is as defined above, m=from 0 to 1000, and m¹≧1 and m²≧3,

in which R¹ is in each case as defined above.One example of a Z³-containing branch unit V³ is, for example:

The polyamino- and/or polyammonium-polysiloxane compounds b1) used maybe solid or liquid at 25° C. In the case that they are liquid at 25° C.,the viscosities of the polysiloxanes b1) mentioned are preferablybetween 500 and 50 000 000 mPa·s at 25° C., preferably from 1000 to 2500 000 mPa·s at 25° C., and at a shear rate gradient of D=1 s⁻¹. Theymay have melting points up to 250° C., but are water-soluble or-dispersible. Their solubility is preferably more than 1 g/l at 25° C.

The component b2) used may be one or more one amino- and/orammonium-polysiloxane compounds b2). As explained above, these containamino or ammonium groups only in the pendent groups. The amino- and/orammonium-polysiloxane compounds b2) are preferably polysiloxanes whichbear primary and/or secondary and/or tertiary amino groups in thependent groups, in which the amino groups may optionally be protonatedor quaternized, and which may optionally contain additional hydrophilicgroups. The amino or ammonium groups mentioned are preferably bonded tothe siloxane skeleton via carbon. The amino- and/orammonium-polysiloxane compounds b2) mentioned are preferablypolyalkylsiloxanes having aminoalkyl- or aminoarylsiloxane units. Theaminoalkyl units may be bonded to the difunctional, trifunctional or themonofunctional end groups, and be part of other oxygen-containingpendent groups, in particular of polyether pendent groups.

The additional hydrophilicizing groups optionally present are preferablythose which derive from polyalkylene oxides and saccharides.

The aminopolysiloxanes mentioned are linear or branched polysiloxaneswhich are formed from siloxy units which are selected from the groupconsisting of:

in which R¹¹ represents organic radicals which may be the same ordifferent with the proviso that at least one of the R¹¹ radicalscontains at least one nitrogen atom.

-   -   The R¹¹ substituents are preferably selected from the group        consisting of:    -   straight-chain, cyclic or branched, saturated, unsaturated or        aromatic hydrocarbon radical which has up to 200 carbon atoms        and may optionally contain one or more groups selected from:    -   —O—,    -   —NR²— where R² may be hydrogen, a monovalent, straight-chain,        cyclic or branched, saturated, unsaturated or aromatic        hydrocarbon radical which has up to 100 carbon atoms, may        contain one or more groups selected from —O—, —NH—, —C(O)— and        —C(S)—, and is optionally substituted by one or more        substituents selected from the group consisting of a hydroxyl        group, an optionally substituted heterocyclic group preferably        containing one or more nitrogen atoms, amino, alkylamino,        dialkylamino, ammonium, polyether radicals and polyether ester        radicals, where, when a plurality of —NR² groups is present,        they may be the same or different,        and the radical may optionally be substituted by one or more        substituents selected from hydroxyl and        where R¹, m, m2 are each as defined above,    -   hydroxyl,    -   a polyether radical which has up to 20 000 carbon atoms and may        optionally bear one or more amino, mono- or dialkylamino, or        arylamino groups,    -   a saccharide-containing organic radical,    -   or two R¹¹ substituents from different siloxy units together        form a straight-chain, branched or cyclic alkanediyl radical        having from 2 to 12 carbon atoms between two silicon atoms,    -   with the proviso that at least one R¹¹ substituent per molecule        contains nitrogen, i.e., constitutes a nitrogen-containing R¹¹        radical.    -   R¹¹ is preferably alkyl, in particular methyl.    -   Preferred R¹¹ radicals which have nitrogen are, for example:        Further preferred amino- and ammonium-containing R¹¹ radicals        are, for example:        Corresponding aminopolysiloxanes having such R¹¹ radicals are        disclosed in WO 02/10256, whose disclosure content belongs to        the present application.        The nitrogen-containing R¹¹ radical is preferably aminopropyl or        aminoethylaminopropyl. Further preferred nitrogen-containing R¹¹        radicals are formed from the reaction of        glycidyloxypropylsiloxanes with mono- or dialkylamines.        Preferred compounds as component b2) are therefore, for example,        aminopolysiloxanes which arise from the reaction of        epoxyalkylsiloxanes with ammonia, primary or secondary amines,        such as those from the reaction of glycidyloxypropylsiloxanes        with mono- or dialkylamines. Preferred alkoxy radicals for R¹¹        are methoxy, ethoxy, propoxy, isopropoxy, butoxy, hexyloxy and        cyclohexyloxy.        Preferred polyether radicals which have up to 20 000 carbon        atoms and may optionally bear one or more amino-, mono- or        dialkylamino, or arylamino groups for R¹¹ include, for example:        Saccharide-containing organic radicals for R¹¹ are, for example:

The preparation of such saccharide-containing polysiloxanes can befound, for example, in DE 4 318 536, DE 4 318 537.

The average degree of polymerization of the polysiloxane moiety of theaminopolysiloxanes b2) used in accordance with the invention, whichresults from Mn, is appropriately from 1 to 3000, preferably from 200 to1000.

The ratio of the nitrogen-free polyorganosiloxane units to thenitrogen-containing polyorganosiloxane units in the aminopolysiloxanesb2) used in accordance with the invention is appropriately from 1:1 to500:1.

The ratio of the polyether- or saccharide-containing polyorganosiloxaneunits to the remaining polyorganosiloxane units may be from 0 to 1.

The typical nitrogen content of the aminopolysiloxanes b2) used inaccordance with the invention is, for example, between 0.005% by weightto 18% by weight, preferably from 0.02% by weight to 5% by weight, morepreferably from 0.02% by weight to 1.5% by weight.

The aminopolysiloxanes b2) used may be solid or liquid at 25° C. In thecase that they are liquid at 25° C., the viscosities of theaminopolysiloxanes b2) used in accordance with the invention arepreferably between 500 to 500 000 mPa·s at 25° C., preferably from 1000to 25 000 mPa·s at 25° C., and at a shear rate gradient of D=1 s⁻¹.

They may have melting points up to 250° C., but are water-soluble or-dispersible. Their solubility is preferably more than 1 g/l at 25° C.

Some of the above-described aminopolysiloxanes b2) used in accordancewith the invention are obtainable, for example, as Wacker Finish® WR1100 and General Electric® SF 1923.

The preferred amount of component b), i.e. b1)+b2), based on the totalamount of the formulation, is from 1 to 30% by weight, preferably from 1to 20% by weight.

The component c) used optionally is one or more silicone-free,preferably cationic, surfactants. It is preferably at least oneconstituent which is selected from nonpolymerized, organic, quaternaryammonium compounds. It preferably comprises hydrocarbon-containingquaternary ammonium salts or amine salts, and the hydrocarbon groups maypreferably contain from 8 to 28 carbon atoms.

Examples of components c) are compounds of the following formula:R¹²R¹³R¹⁴R¹⁵N⁺X⁻

in which R¹², R¹³, R¹⁴ and R¹⁵ are each independently selected from thegroup consisting of: C₁-C₂₈-alkyl, alkenyl, hydroxyalkyl, benzyl,alkylbenzyl, alkenylbenzyl, benzylalkyl and benzylalkenyl, and X is ananion. The hydrocarbon groups R¹², R¹³, R¹⁴ and R¹⁵ may independently bepolyalkoxylated, preferably polyethoxylated or polypropoxylated, morepreferably with groups of the general formula (C₂H₄O)_(y)H where y=from1 to 15, preferably from 2 to 5. Not more than one of the R¹², R¹³, R¹⁴and R¹⁵ groups should be benzyl. The R¹², R¹³, R¹⁴ and R¹⁵ groups mayeach independently contain one or more, preferably two, ester(—[—O—C(O)—]; [—C(O)—O—]) and/or amido groups (—[CO—N(R 2)—];[—N(R¹²)—CO—]) in which R¹² is as defined above. The anion X may beselected from halides, methosulfate, acetate and phosphate, preferablyfrom halides and methosulfate. Further examples of component c) aretetraorgano-substituted quaternary ammonium compounds having one or twolong-chain C8 to C28 hydrocarbon radicals and two or three short-chainC1 to C6 hydrocarbon radicals. The long-chain radicals are preferablyC12 to C20 chains and the short-chain radicals are preferably methyl,ethyl, propyl, butyl, hexyl, phenyl and hydroxyethyl, 2-hydroxypropyl.Preferred counterions are Cl⁻, Br⁻, CH₃OSO₃ ⁻, C₂H₅OSO₃ ⁻, NO₃ ⁻, HCOO⁻and CH₃COO⁻.

Examples include:

-   dodecylethyldimethylammonium bromide-   didodecyldimethylammonium bromide.

In the cationic surfactants which contain only one long-chainhydrocarbon group R¹², the chain length of the long-chain hydrocarbongroup is preferably from 12 to 15 carbon atoms, and the short-chainradicals R¹³, R¹⁴ and R¹⁵ are preferably methyl and hydroxyethyl.

In the cationic surfactants which contain two, three or even fourlong-chain hydrocarbon groups, the chain length of the long-chainhydrocarbon groups is preferably from 12 to 28 carbon atoms.

Preferred ester-containing surfactants have the formula:{(R¹⁶)₂N[(CH₂)_(z)ER¹⁷]₂}⁺X⁻in which R¹⁶ is independently selected from C₁₋₄ alkyl, hydroxyalkyl orC₂₋₄ alkenyl; and in which R¹⁷ is independently selected from C₈₋₂₈alkyl or alkenyl groups; E is an ester group, i.e. —OC(O)— or —C(O)O—, zis an integer from 0 to 8 and X⁻ is as defined above. They contain twoor three short-chain C1 to C6 hydrocarbon radicals. The one or two longalkyl radicals per molecule derive from fatty acids of lengths from C8to C26, preferably from C10 to C20, especially from C12 to C18. Thefatty acids or the cuts of the chain length ranges mentioned may besaturated fatty acids, unsaturated fatty acids, hydroxy-substitutedfatty acids or mixtures thereof. Examples of the acids mentioned arelauric acid, myristic acid, palmitic acid, stearic acid, oleic acid andricinoleic acid. Further examples are tallow fatty acid and coconutfatty acid cuts. They are bonded to the quaternized nitrogen preferablyvia oxyethyl, 2-oxypropyl or 1,2-dioxypropyl or oligooxyethylenespacers. The short-chain radicals are preferably methyl, ethyl, propyl,butyl, hexyl, phenyl and hydroxyethyl, 2-hydroxypropyl. Preferredcounterions are Cl⁻, Br⁻, CH₃OSO₃ ⁻, C₂H₅OSO₃ ⁻, NO₃ ⁻, HCOO⁻ andCH₃COO⁻.Examples include

-   (tallow fatty acid oxyethyl)trimethylammonium methosulfate-   (coconut fatty acid pentaethoxy)trimethylammonium methosulfate-   di(tallow fatty acid oxyethyl)dimethylammonium chloride-   di(tallow fatty acid oxyethyl)hydroxyethylmethylammonium    methosulfate-   di(tallow fatty acid 2-oxypropyl)dimethylammonium methosulfate-   1,2-(ditallow fatty acid)oxy-3-trimethylpropaneammonium chloride

A further type of preferred ester-containing cationic surfactants can berepresented by the following formula:

{(R¹⁶)₃N(CH₂)_(z)CH [O(O)CHR¹⁷] [CH₂O(O)CR¹⁷]}⁺X⁻, in which R¹⁶, R¹⁷, X,and z are each as defined above.

A further group of cationic surfactants c) is those of the formulaR¹⁸A(CH₂)₂₋₄NR¹⁹R²⁰ in which R¹⁸ is C₆-C₁₂ alkyl;

A is a divalent group which is selected from —NH—, —CONH—, —COO— or —O—,or A may be absent. R¹⁹ and R²⁰ are each independently selected from thegroup consisting of H, C₁-C₁₄ alkyl or (CH₂—CH₂—O(R²¹)) in which R²¹ isH or methyl.

Particularly preferred surfactants of this type are decylamine,dodecylamine, C₈-C₁₂ bis(hydroxyethyl)amine, C₈-C₁₂bis(hydroxypropyl)amine, C₈-C₁₂ amidopropyldimethylamine or saltsthereof.

Further surfactants include: fatty acid amides of the formulaR²²C(O)N(R²³)₂ wherein R²² is an alkyl group having from 8 to 28 carbonatoms and R²³ is in each case a short-chain radical, preferably selectedfrom hydrogen, C₁-C₆ alkyl and hydroxyalkyl. It is also possible to useC₈-C₂₈ N-alkylpolyhydroxy fatty acid amides. Typical examples include:C₁₂-C₁₈ N-methylglucamides (see WO 92/06154). Other sugar derivativesinclude, for example, C₈-C₂₈ N-(3-methoxy-propyl)glucamide. Theselikewise have two or three short-chain C₁ to C₆ hydrocarbon radicals.The one or two long alkyl radicals per molecule derive from fatty acidsof lengths C₈ to C₂₆, preferably C₁₀ to C₂₀, especially C₁₂ to C₁₈. Thefatty acids or the cuts of the chain length ranges mentioned maylikewise be saturated fatty acids, unsaturated fatty acids,hydroxy-substituted fatty acids or mixtures thereof. Examples of theacids mentioned are lauric acid, myristic acid, palmitic acid, stearicacid, oleic acid and ricinoleic acid. Further examples are tallow fattyacid and coconut fatty acid cuts. They are bonded to the quaternizednitrogen preferably via amidoethyl and 3-amidopropyl spacers. Theshort-chain radicals are preferably methyl, ethyl, propyl, butyl, hexyl,phenyl and hydroxyethyl, 2-hydroxypropyl. They may also alternatively becyclic radicals such as imidazolinium radicals into which fatty alkylsubstituents have optionally additionally been incorporated. Preferredcounterions are Cl⁻, Br⁻, CH₃OSO₃ ⁻, C₂H₅OSO₃ ⁻, NO₃ ⁻, HCOO⁻ andCH₃COO⁻.

Examples include

-   (undecylenic acid amidopropyl)trimethylammonium methosulfate-   (ricinoleic acid amidopropyl)trimethylammonium methosulfate-   1-methyl-1-(tallow fatty acid amidoethyl)-2-(tallow fatty    alkyl)imidazolinium methosulfate-   1-methyl-1-oleylamidoethyl-2-oleylimidazolinium methosulfate-   1,1-ethylenebis(1-methyl-2-(tallow fatty alkyl)imidazolinium)    methosulfate.

In addition to the quaternary ammonium compounds, amine salts may alsofind use. These are salts of primary, secondary or tertiary amines withinorganic or organic acids.

In these amine salts, the nitrogen is substituted by one or twolong-chain C₈ to C₂₈ hydrocarbon radicals, one to three hydrogen atomsand optionally one or two short-chain C₁ to C₆ hydrocarbon radicals. Theone or two long alkyl radicals per molecule derive, for example, fromfatty amines or fatty acids of lengths C8 to C26, preferably C10 to C20,especially C12 to C18. Preferred counterions are Cl⁻, Br⁻, CH₃OSO₃ ⁻,C₂H₅OSO₃ ⁻, NO₃ ⁻, HCOO⁻ and CH₃COO⁻.

To increase the hydrophilicity, the fatty amines used may beethoxylated. One example is the ethoxylated stearylamine derivativeCH₃(CH₂)₁₇N⁺H[(CH₂CH₂O)₅H]₂ Cl⁻.

The fatty acids or the cuts of the chain length ranges mentioned may bethe saturated fatty acids, unsaturated fatty acids, hydroxy-substitutedfatty acids or mixtures thereof, which have already been described.Examples of the acids mentioned are lauric acid, myristic acid, palmiticacid, stearic acid, oleic acid and ricinoleic acid. Further examples aretallow fatty acid and coconut fatty acid cuts. They are bonded to theamine salt nitrogen preferably via oxyethyl, 2-oxypropyl,1,2-dioxypropyl spacers in the case of esters, and preferably viaamidoethyl and 3-amidopropyl spacers in the case of amides. Theshort-chain radicals are preferably methyl, ethyl, propyl, butyl, hexyl,phenyl and hydroxyethyl, 2-hydroxypropyl. Preferred counterions are Cl⁻,Br⁻, CH₃OSO₃ ⁻, C₂H₅OSO₃ ⁻, NO₃ ⁻, HCOO⁻ and CH₃COO⁻.

Examples include

-   stearic acid triethanolamine derivative:-   CH₃(CH₂)₁₆C(O)OCH₂CH₂N⁺(CH₂CHOH)₂ Cl⁻-   stearamide derivative CH₃(CH₂)₁₆CONHCH₂CH₂N⁺H₂CH₂CH₂N⁺H₃ 2Cl⁻-   stearamide derivative CH₃(CH₂)₁₆CONHCH₂CH₂N⁺H₂CH₂CH₂OH Cl⁻-   palmitamide derivative CH₃(CH₂)₁₄CONHCH₂CH₂CH₂N⁺H(CH₃)₂ Cl⁻.

The amount of the optionally used component c), based on the totalamount of the formulation, is from 0 to 30% by weight, preferably from 0to 10% by weight. If component c) is present in the formulation, theamount is preferably between 0.01% by weight and 15% by weight, morepreferably from 1 to 10% by weight.

Component c) in the inventive formulations has the function of improvingthe emulsifiability of component a) and in some cases of increasing thesubstantivity.

The optionally used coacervate formation agents as per component d) areappropriately cationic copolymers which are based on natural orsynthetic polymer structures. They differ in this respect from thesilicone-free cationic surfactants of component c) which are not basedon polymer structures. Combinations of natural and synthetic polymersare likewise possible. Coacervate formation agents means complex chargedanions or cations which each form a complex salt with changeddissolution behavior with a polymer or colloid particle charged in theopposite sense.

The term “coacervate phase” as used in accordance with the inventionembraces all types of discontinuous phases, as described, for example,in “B. Jonsson, B. Lindman, K. Holmberg & B. Kronberb, “Surfactants andPolymers In Aqueous Solution”, John Wiley & Sons, 1998” and in “L.Piculell & B. Lindman, Adv. Colloid Interface Sci., 41 (1992)”. Themechanism of the coacervation and its specific influences are described,for example, in “Interfacial Forces in Aqueous Media”, C. J. van Oss,Marcel Dekker, 1994, page 245 to 271. The term “coacervate phase” isoccasionally also referred to in the literature as “complex coacervatephase” or as “associated phase separation”.

The coacervate phase formation agent as per component d), optionallypresent in the invention formulation, leads, for example in the eventthat it comes into contact with anionic surfactants or anionic groups ofany other components, for example in the application of the inventiveformulation, such as in laundry detergent formulations, fiber treatmentformulations or in the treatment of pretreated substrate surface(anionic assistants or soil particles), to the formation of coacervatephases.

This phase formation is visible, for example, microscopically usingdyes.

For the substances as per d), the term “cationic” generally relates toprotonated amino compounds or else quaternary ammonium compounds(tetraorganoammonium compounds).

Natural copolymers derive preferably from cellulose, starch or chitosan.As particularly advantageous natural copolymers, emphasis should begiven to the guar gum derivatives modified by quaternary ammoniumgroups. These are commercially available as the Jaguar types fromRhône-Poulenc (Rhodia).

Synthetic copolymers are based preferably on cationic structures such aspolyvinylamines, polyethyleneimines and polydimethyldiallylammoniumhalides. Alternatively, it is possible to use cationically modifiedmaterials based, for example, on polyvinylpyrrolidone, polyacrylamide,polymethylacrylamide, polyvinylimidazole and aminoalkylimidazolecopolymers.

Particularly advantageous within this group are high molecular weightpoly(vinylamine-vinylformamide) copolymers and high molecular weightpolyethyleneimines.

Generally, high molecular weight natural or synthetic coacervateformation agents are to be preferred over low molecular weightstructurally analogous compounds.

A third material group is that of complexes of polycationic andpolyanionic compounds, i.e. complex salts.

Preference is given in this context to combinations of natural polymersand synthetic polymers. Specifically, they are combinations of anionicnatural polymers with cationic synthetic polymers. The pairing ofcationic natural polymer with anionic synthetic polymer is likewisepossible. Examples of preferred combinations arecarboxymethylcellulose/polyethyleneimine,carboxymethyl-cellulose/polyvinylamine, chitosan/polystyrenesulfonicacid, chitosan/polyacrylic acid, chitosan/polymethacrylic acid.

Preference is further given to combinations of two oppositely chargednatural polymers or synthetic polymers. Examples thereof are thecarboxymethyl-cellulose/chitosan, polyethyleneimine/polyacrylic acid andpolyvinylamine/polystyrenesulfonic acid combinations.

The polycationic compounds may be used in the form of the bases or saltsof monovalent anions. The polyanionic compounds may be used in the formof the acids or salts of monovalent cations.

Synthetic polycationic and polyanionic compounds may be used in the formof their copolymers, which allows their charge density to be adjustedvariably.

When the complexes considered above are used, it has to be ensured thattheir net charge is cationic. This means that, irrespective of thespecific pairing, an excess of amino or ammonium groups relative to theanionic groups such as carboxylic acid, sulfonic acid, sulfuricmonoesters and salts thereof is present.

As a result of the complexation of polycationic with polyanioniccompounds of the above-described type, the molar mass of the coacervateformation agent rises in a desired manner.

If the coacervate formation agent d) is present in the inventiveformulation, its preferred amount is from 0.001 to 5% by weight, morepreferably from 0.1 to 1% by weight, based on the total amount of theformulation.

The component e) used in the inventive formulation comprises one or morecarrier substances. These are selected preferably from solid carriersubstances f) and/or liquid carrier substances g). In the context of thepresent invention, this means that the liquid carriers are liquid at 40°C., and the solid carriers are solid at 40° C.

Preferred liquid carriers g) include aqueous and nonaqueous carriers andmay include: water alone or organic solvents, preferably water-solubleorganic solvents alone and/or mixtures thereof with water. Preferredorganic solvents include: monoalcohols, diols, polyols such as glycerol,glycol, polyethers such as polyalkylene glycols such as polyethyleneglycols and mixtures thereof, also with water. Particular preference isgiven to mixtures of solvents, in particular mixtures of lower aliphaticalcohols such as ethanol, propanol, butanol, isopropanol and/or diolssuch as 1,2-propanediol or 1,3-propanediol; or mixtures thereof withglycerol. Suitable alcohols include in particular C₁-C₄ alcohols.Preference is given to 1,2-propanediol.

The liquid carrier g) is appropriately present in the inventiveformulation, based on the total amount of the formulation, in an amountof from 0 to 95% by weight, preferably from 0 to 65% by weight, morepreferably from 0 to 55% by weight. When the liquid carrier g) ispresent in the inventive formulation, its preferred amount is more than5% by weight, more preferably more than 10% by weight, most preferablyfrom more than 30 to 70% by weight, more preferably to 60% by weight.

The solid carrier f) used as component e) is preferably selected fromcompounds which are solid at 40° C. They are more preferably compoundswhich are selected from the group of the water-soluble compounds whichhave a solubility in water of at least 100 grams/liter at 20° C.Examples of the solid carriers include:

Inorganic or organic salts, polyhydroxy compounds, saccharides, amidessuch as urea, and relatively high molecular weight polyethylene oxides.The solid carriers f) are preferably compounds which have no significantinterface-active action in the sense of surfactants. Examples ofinorganic salts are sodium chloride, potassium chloride, sodiumcarbonate, sodium sulfate. An example of an organic salt is sodiumacetate. Examples of polyhydroxy compounds and saccharides which can beused in accordance with the invention are pentaerythritol, sorbitol,glucamine, N-methylglucamine. Amide derivatives which can be used inaccordance with the invention are, for example, urea and stronglyhydrophilic, saccharide-modified amide derivatives such asethylenediaminebisgluconamide, 1,3-propylenediaminebisgluconamide,1,2-propylenediaminebisgluconamide, diethylenetriaminebisgluconamide,dipropylenetriaminebisgluconamide,N-methyldipropylenetriaminebisgluconamide,N,N-dimethylethylenediaminegluconamide,N,N-dimethylpropylenediaminegluconamide. The latter saccharide-modifiedderivatives are obtainable by regioselective reaction of the primaryamino groups of the corresponding amines with saccharidecarboxylic acidlactones such as gluconolactone or glucopyranosylarabinolactone (DE 4318 536, DE 4 318 537).

The solid carrier f) is appropriately present in the inventiveformulation, based on the total amount of the formulation, in an amountof from 0 to 95% by weight, preferably from 0 to 65% by weight, morepreferably from 0 to 55% by weight. When the solid carrier f) is presentin the inventive formulation, its preferred amount is more than 5% byweight, more preferably more than 10% by weight, most preferably frommore than 30 to 70% by weight, more preferably to 60% by weight.

The solid carrier f) and the liquid carrier g) may be present in anyratios relative to one another. The selection of the ratio depends uponwhether liquid, pasty or solid compositions of the formulation aredesired.

Depending on the fields of use, the inventive formulation may comprisefurther other ingredients or assistants in addition to theabove-described components a) to g).

In the case of use in laundry detergents, for example, what are known asbuilders, for example zeolites, silicates, polyphosphates, alkali metalcitrates, alkali metal 2,2-oxydisuccinates, alkali metalcarboxymethyloxysuccinates, alkali metal nitrilotriacetates and sodiumcarbonate, enzymes, defoamers such as silicone compounds and stabilizersmay be present. The stabilizers serve, for example, to stabilize thecomponent b) by preventing its coagulation and sedimentation. Thestabilizers are, for example, gums and other polysaccharides, forexample carrageenan gum, other thickeners or rheology additives. Thestabilizer is preferably a crystalline hydroxyl-containing compound suchas trihydroxystearin, a hydrogenated oil or a derivative thereof.

Further assistants which may be present in particular in laundrydetergents are coupling agents such as hexylamine, octylamine,nonylamine, their C1-C3 secondary or tertiary analogs, and alkanediols.

Further assistants which may be present in laundry detergents inparticular are fragrances which adhere to the substrates, chelatingagents, other surface-active substances.

The preparation of the inventive formulation may include, for example,the preparation of a homogeneous base mixture a)+b) and the introductionof the optional components c) to e).

In an advantageous embodiment of the invention, the components a) and b)are initially mixed homogeneously to give a premixture, optionally withaddition of parts of the carrier substance e). In the context of theinvention, homogeneous means substantially dissolved or elsetransparently finely dispersed. The optional component c), for example,may subsequently be introduced into this homogeneous premixture.Depending on the structure of the premixture components a) and b) and ofthe component c) this introduction may lead in turn to a homogeneousmixture or else to a visibly more coarsely disperse distribution of c)in the a)+b) premixture. Depending on the end application, d),(optionally further) e), i.e. f) and/or g), may be introduced into thismixture.

In a further preferred embodiment of the invention, a solution of c) inwater e) or a solution of d) in water e) or a mixture of c) and d) isintroduced into the a)+b) premixture. An addition of c)+d)+e) to thea)+b) premixture likewise lies within the scope of the invention.

It is possible using these different mixing strategies to influence themicroscopic distribution of the components in the overall system andthus the product properties.

The invention further relates to the use of the inventive formulation incosmetic formulations, in laundry detergents or for the surfacetreatment of substrates.

The invention further relates to the use of the inventive formulationfor fiber treatment or fiber finishing.

The invention further relates to the use of the inventive formulationfor the treatment of textiles and other natural and synthetic fiberlikematerials including paper.

The inventive formulations are particularly suitable for use in thepresence of anionic surfactants, in particular in laundry detergentformulations or in the treatment of pretreated fibers.

The invention further relates to the use of the inventive formulation asa softener.

The above-described mixtures constitute formulations which are suitablefor the treatment of textiles and other natural and synthetic fiberlikematerials, especially in the presence of anionic surfactants fromlaundry detergent formulations or compositions for fiber pretreatment.For this purpose, the inventive formulations may be incorporateddirectly into laundry detergents or else metered separately into therunning washing process. As a result of the use of the inventiveformulations during the washing process, a silicone-typical softness,improved elasticity and reduced creasing tendency are imparted to thetreated substrates.

In addition, the formulations described may find use as a constituent ofseparate softener systems after the washing of fibers and textiles. Inaddition, the formulations described may find use for the surfacetreatment of substrates such as natural and synthetic fibers, includingpaper and textiles, as a constituent of systems for initial textilefinishing, as an ironing aid and composition for the prevention andreversal of textile creases. It is also possible to introduce theinventive formulation into cosmetic systems for the treatment of hairand skin.

The inventive formulations may be present in liquid, including pasty, orsolid form. In addition, the formulation may be present in encapsulatedform or in a liquid or solid matrix.

A preferred formulation of the present invention contains:

-   -   a): from 5 to 99, preferably from 10 to 80, more preferably from        10 to 40,    -   b): from 1 to 95, preferably from 1 to 30, more preferably from        1 to 20,    -   c): from 0 to 10, preferably from 1 to 10,    -   d): from 0 to 1, preferably from 0.1 to 1,    -   e): from 0 to 70, preferably from 30 to 70,    -   the data being percentages by weight based on the total weight        of the formulation.

EXAMPLES Example 1

(Preparation of the Quat According to WO 02/10259)

A 1 liter three-neck flask is initially charged at room temperature with24 g of water and 4.18 g (0.048 mol of tertiary amino groups) ofN,N,N′,N′-tetramethyl-1,6-hexanediamine and 3.8 g (0.012 mol of primaryamino groups) of an alkylene oxide derivative, obtainable under thetrade name Jeffamine® ED 600, of the structureH₂NCH(CH₃)CH₂[OCH₂CH(CH₃)]_(a)(OCH₂CH₂)₉[OCH₂CH(CH₃)]_(b)NH₂where a+b=3.6.

Within 5 minutes, 12.0 g (0.03 mol) of dodecanoic acid in the form of a50% solution in 2-propanol and 1.8 g (0.03 mol) of acetic acid areadded. After the mixture has been heated to 50° C., 194.1 g (0.06 mol ofepoxy groups) of an epoxysilane of the average composition

and 30 ml of 2-propanol are added dropwise within 30 minutes. Theyellow, opaque mixture is heated to reflux temperature for 6 hours.After all constituents which are volatile up to 100° C./2 mmHg underreduced pressure have been removed, 204 g of a colorless, opaquematerial are obtained as component b1), which contains the followingstructural elements:

In the above formula, the Q, V¹ and V² repeat units are also includedfor the purposes of illustration. The molar ratio of the V¹-containingpolysiloxane-free diamino components and the V²-containing long-chainpolysiloxane-containing diepoxy components of 1:1 results in a ratio ofV²/V¹ of 1:1.

Example 2

(Preparation of the Quat According to WO 02/10257)

a) 211.1 g (0.15 mol of epoxy groups) of an epoxysilane of the averagecomposition

and 15.2 g (0.15 mol) of N-methylpiperazine are dissolved in 225 ml ofisopropanol and heated to 90° C. for 4 hours. After the end of thereaction, the solvent was removed by distillation in a water-jet vacuumand finally in an oil-pump vacuum. 217 g of a clear, yellowish productof the structure

were obtained.

13C NMR: Substructure shift (ppm) — C H(OH)— 66.07 —CH(OH)— C H₂—N—60.74 —CH(OH)—CH₂—N— C H₂— 53.20 —CH(OH)—CH₂—N—CH₂— C H₂— 55.10 C H₃—N═45.87b) 200 g (1.21 mol) of triethylene glycol monomethyl ether wereinitially charged at room temperature, 20° C., under nitrogen. Withvigorous stirring, 151 g (1.34 mol) of chloroacetyl chloride were addeddropwise within 30 minutes. During the dropwise addition, thetemperature rose to 90° C. and intensive HCl evolution set in. Oncompletion of the dropwise addition, the mixture was heated to 130° C.for 30 minutes. Subsequently, all constituents which boiled up to 130°C. and at 20 hPa were distilled off. 301 g of a light yellow, viscousliquid of the composition

were obtained.

The purity of the ester, determined by gas chromatography, was 99%.

¹³C NMR: Substructure shift (ppm) Cl C H₂ 40.8 ClCH₂— C (O)— 167.3ClCH₂—CH₂—C(O)—O C H₂— 65.2 ClCH₂—CH₂—C(O)—OCH₂— C H₂— 68.7 —CH₂—O C H₃58.8c) 19.61 g (6.5×10⁻³ mol) of the α,ω-aminosiloxane as per example 4a)and 3.12 g (1.3×10⁻² mol) of the chloroacetic ester as per example 4b)were dissolved in 50 ml of isopropanol under nitrogen and heated toreflux temperature for 12 hours. After the reaction had ended, allconstituents which boiled up to 70° C. and at 20 hPa were removed. 19.7g of a yellowish-light brown viscous oil of the formula:

were obtained as component b1). Gas chromatography detected aquantitative conversion of the ester.

¹³C NMR: Substructure shift (ppm) — C H(OH)— 65.9/66.1 —CH(OH)— C H₂—N—52.6 —CH(OH)—CH₂—N— C H₂— 45.4 —CH(OH)—CH₂—N—CH₂— C H₂— 60.5/60.6—CH(OH)—CH₂—N—CH₂—CH₂—N⁺— C H₂— 61.4 —CH(OH)—CH₂—N—CH₂—N⁺—CH₂— C (O)—169.6/169.9 C H₃—N⁺ ═ 52.9 —CH₂—O C H₃ 58.6

According to the ¹³C NMR spectrum, the quaternization proceededselectively on the methyl-substituted nitrogen atoms.

Example 3

153 g (1.5 mol) of H₂NCH₂CH₂CH₂N(CH₃)₂ are initially charged undernitrogen in a four-neck flask. Within 15 minutes, 412.3 g (1.5 mol) ofpalmitoyl chloride are added dropwise. The addition is regulated in sucha way that the mixture remains in the temperature range from 100° C. to120° C. After the addition has been completed, vacuum is applied brieflyin order to degas the white-yellowish viscous mass which has formed. 123g (1.5 mol) of sodium acetate are added to this viscous mass at 100° C.After cooling, 556 g of a white-yellowish hard mass are obtained.

Composition:CH₃(CH₂)₁₄C(O)NHCH₂CH₂CH₂N⁺H(CH₃)₂Cl⁻+CH₃COONa

Example 4

Starting from tetrameric cyclodimethylsiloxane or acyclosiloxanepolydimethylsiloxanediol mixture andaminopropylmethyldiethoxysilane, aminopropyldimethylethoxysilane,optionally addition of water traces and hexamethyldisiloxane, knownalkali-catalyzed equilibration and condensation with elimination ofethanol provides an aminosiloxane b2) of the following average relativeformula:

According to the ¹H NMR spectrum, this material still contains traces ofethoxy groups.

Example 5

The following formulations are prepared: Formulation 1 Formulation 214.5 g of siloxane quat as per 14.5 g of aminosiloxane as per example 1example 4 3.3 g of siloxane quat as per 3.3 g of siloxane quat as perexample 2 example 2 28.9 g of polydimethylsiloxane 28.9 g ofpolydimethylsiloxane viscosity 1 000 000 mPa · s viscosity 1 000 000 mPa· s 3.3 g of amine salt as per 3.3 g of amine salt as per example 3example 3 50 g of water 50 g of water Formulation 3 Formulation 4 14.5 gof siloxane quat as 14.5 g of aminosiloxane as per example 1 per example4 3.3 g of siloxane quat as 3.3 g of siloxane quat as per example 2 perexample 2 28.9 g of polydimethylsiloxane 28.9 g of polydimethylsiloxaneviscosity 1 000 000 mPa · s viscosity 1 000 000 mPa · s 3.3 g of aminesalt as per 3.3 g of amine salt as per example 3 example 3 50 g ofwater + 0.74 g of a 50 g of water + 0.74 g of a cationic guar gum (MW425 000; cationic guar gum (MW 425 000; 0.7 mmol/g of N⁺) 0.7 mmol/g ofN⁺)

To prepare the formulations, the two silicone quats for F1 or theaminosiloxane and the silicone quat for F2 are initially mixed with oneanother. The polydimethylsiloxane is stirred homogeneously into thesemixtures. Subsequently, the amine salt is finely distributed in thesepremixtures. An opaque mass is formed in each case. Finally, the wateris stirred slowly into F1 and F2, so that white emulsion-like liquidsare obtained.

The aqueous guar gum solution is finally stirred into the formulationsF3 and F4.

Example 6

To demonstrate the softening properties, wash experiments are carriedout in a drum washing machine with a pulverulent (Dash® 2in1) laundrydetergent and a liquid (Ariel liquid®) laundry detergent. Washexperiment W1 40° C., 20 min, then 5× rinse 110 g of Dash ® 2in1 matrixwithout bentonite 2 kg of washing (1850 g of ballast material + 5 terryswatches, 150 g in total) 10 l of water in the machine 13.5 g offormulation F1 introduced separately directly after Dash 2in1 matrixWash experiment W2 Wash experiment W3 40° C., 20 min, then 5× rinse 40°C., 20 min, then 5× rinse 110 g of Dash ® 2in1 matrix 75 g of Arielliquid without bentonite 2 kg of washing (1850 g of ballast 2 kg ofwashing (1850 g of ballast material + 5 terry swatches, material + 5terry swatches, 150 g in total) 150 g in total) 10 l of water in themachine 10 l of water in the machine 13.5 g of formulation F2 13.5 g offormulation F2 introduced introduced separately directly before the washexperiment in Ariel after Dash 2in1 matrix liquid Wash experiment W4Wash experiment W5 40° C., 20 min, then 5× rinse 40° C., 20 min, then 5×rinse 110 g of Dash ® 2in1 matrix 75 g of Ariel liquid without bentonite2 kg of washing (1850 g of ballast 2 kg of washing (1850 g of ballastmaterial + 5 terry swatches, material + 5 terry swatches, 150 g intotal) 150 g in total) 10 l of water in the machine 10 l of water in themachine 13.5 g of formulation F3 13.5 g of formulation F4 introducedintroduced separately directly before the wash experiment in Ariel afterDash 2in1 matrix liquidThe 5 terry swatches softened by F1 in wash experiment W1 were comparedwith 5 swatches which had been washed identically with ‘Ariel® liquid’alone.

-   The 5 terry swatches softened by F2 in wash experiment W2 were    compared with 5 swatches which had been washed identically with    Ariel liquid alone.-   The 5 terry swatches softened by F2 in wash experiment W3 were    compared with 5 swatches which had been washed identically with    Ariel liquid alone.-   The 5 terry swatches softened by F3 in wash experiment W4 were    compared with 5 swatches which had been washed identically with    Ariel liquid alone.-   The 5 terry swatches softened by F4 in wash experiment W5 were    compared with 5 swatches which had been washed identically with    Ariel liquid alone.

On a scale from 0 to 4 points, i.e. 1=very good, the swatches washed inaccordance with the invention achieved the following scores: ExperimentW1 W2 W3 W4 W5 Formulation F1 F2 F2 F3 F4 Detergent Dash 2in1 Dash 2in1Ariel liquid Dash 2in1 Ariel liquid Points +1.68 +1.77 +1.80 1.30 1.45Testers 4 4 4 4 4

1. A formulation comprising: a) at least one nitrogen-free polysiloxanecompound, b) at least one polyamino- and/or polyammonium-polysiloxanecompound b1) which is selected from polysiloxane compounds which containat least one unit of the formula (I):-[Q-V]—  (I) in which Q is selected from the group consisting of: —NR—,—NR⁺R₂— a saturated or unsaturated diamino-functional heterocycle of theformulae:

an aromatic diamino-functional heterocycle of the formula:

a trivalent radical of the formula:

a trivalent radical of the formula

a tetravalent radical of the formula

in which R in each case is hydrogen or a monovalent organic radical,where Q is not bonded to a carbonyl carbon atom, V is at least oneconstituent which is selected from the group consisting of V¹, V² andV³, where V² is selected from divalent or trivalent, straight-chain,cyclic or branched, saturated, unsaturated or aromatic hydrocarbonradicals having up to 1000 carbon atoms (not counting the carbon atomsof the polysiloxane radical Z² defined below) and may optionally containone or more groups selected from —O—, —CONH—, —CONR²—, in which R² ishydrogen, a monovalent, straight-chain, cyclic or branched, saturated,unsaturated or aromatic hydrocarbon radical having up to 100 carbonatoms, may contain one or more groups selected from —O—, —NH—, —C(O)—and —C(S)—, and may optionally be substituted by one or moresubstituents selected from the group consisting of a hydroxyl group, anoptionally substituted heterocyclic group preferably containing one ormore nitrogen atoms, amino, alkylamino, dialkylamino, ammonium,polyether radicals and polyether ester radicals, where, when a pluralityof — CONR²— groups is present, they may be the same or different, —C(O)—and —C(S)—, and the radical V² may optionally be substituted by one ormore hydroxyl groups, and the radical V² contains at least one group-Z²- of the formula

in which R¹ may be the same or different and is selected from the groupconsisting of: C₁ to C₂₂ alkyl, fluoro(C₁-C₁₀)alkyl and C₆-C₁₀ aryl, andn₁=20 to 1000, V¹ is selected from divalent, straight-chain, cyclic orbranched, saturated, unsaturated or aromatic hydrocarbon radicals whichhave up to 1000 carbon atoms and may optionally contain one or moregroups selected from —O—, —CONH—, —CONR²—, in which R² is as definedabove, where the R² groups in the V¹ and V² groups may be the same ordifferent, —C(O)—, —C(S)— and -Z¹-, where -Z¹- is a group of the formula

in which R¹ is as defined above, where the R¹ groups in the groups V¹and V² groups may be the same or different, and n₂=0 to 19, and theradical V¹ may if desired be substituted by one or more hydroxyl groups,V³ is a trivalent or higher-valency, straight-chain, cyclic or branched,saturated, unsaturated or aromatic hydrocarbon radical which has up to1000 carbon atoms, may optionally contain one or more groups selectedfrom -0-, —CONH—, —CONR²—, in which R² is as defined above, —C(O)—,—C(S)—, -Z¹- which is as defined above, -Z²- which is as defined aboveand Z³, where Z³ is a trivalent or higher-valency organopolysiloxaneunit, and may optionally be substituted by one or more hydroxyl groups,where, in said polysiloxane compound, in each case one or more V¹groups, one or more V² groups and/or one or more V³ groups may bepresent, with the proviso that said polysiloxane compound contains aplurality of V² groups, that said polysiloxane compound contains atleast one V¹, V² or V³ group which contains at least one -Z¹-, -Z²— orZ³ group, and that the tri- and tetravalent Q radicals either serve tobranch the main chain formed from Q and V, so that the valencies whichdo not serve for bonding in the main chain bear further branches formedfrom -[Q-V]— units, or the tri- and tetravalent Q radicals are saturatedwith V³ radicals within a linear main chain without formation of abranch, and wherein the positive charges resulting from ammonium groupsare neutralized by organic or inorganic acid anions, and acid additionsalts thereof, and optionally at least one amino- and/orammonium-polysiloxane compound b2) c) optionally one or moresilicone-free surfactants, d) optionally one or more coacervate phaseformation agents, e) optionally one or more carrier substances.
 2. Theformulation as claimed in claim 1, characterized in that it contains,based on the total amount of components a) and b), from 5 to 99% byweight of component a) and from 1 to 95% by weight of component b). 3.The formulation as claimed in claim 1, in which the component e) isselected from solid carrier substances f) and/or liquid carriersubstances g).
 4. The formulation as claimed in claim 1, characterizedin that it contains, based on 100 parts by weight of components a) andb), from 0 to 1500 parts by weight of components c), d) and e).
 5. Theformulation as claimed in claim 1, characterized in that it contains,based on 100 parts by weight of components a) and b), from 0 to 70 partsby weight of component c).
 6. The formulation as claimed in claim 1,characterized in that it contains, based on 100 parts by weight ofcomponents a) and b), from 0 to 10 parts by weight of component d). 7.The formulation as claimed in claim 1, characterized in that itcontains, based on 100 parts by weight of components a) and b), from 0to 710 parts by weight of component f).
 8. The formulation as claimed inclaim 1, characterized in that it contains, based on 100 parts by weightof components a) and b), from 0 to 710 parts by weight of component g).9. The formulation as claimed in claim 1, characterized in thatcomponent a) is at least one constituent which is selected from thegroup consisting of: straight-chain, cyclic, branched and partiallycrosslinked polyorganosiloxanes.
 10. The formulation as claimed in claim1, characterized in that the amino- and/or ammonium-polysiloxanecompound b2) is a polysiloxane compound which contains amino and/orammonium groups in the pendent groups of a polyorganosiloxane mainchain.
 11. The formulation as claimed in claim 1, characterized in thatthe silicone-free surfactant as component c) is at least one constituentwhich is selected from nonpolymerized, organic, quaternary ammoniumcompounds.
 12. The formulation as claimed in claim 1, characterized inthat the coacervate phase formation agent as component d) comprises atleast one constituent which is selected from cationic, silicone-freepolymer compounds.
 13. The formulation as claimed in claim 3,characterized in that the solid carrier substance f) is at least oneconstituent which is selected from the group of the water-solublecompounds which have a solubility in water of at least 100 grams/literat 20° C.
 14. The formulation as claimed in claim 3, characterized inthat the liquid carrier substance g) is at least one constituent whichis selected from the group consisting of water and water-miscibleorganic solvents.
 15. The formulation as claimed in claim 1,characterized in that it is solid or liquid at 40° C.
 16. A process forpreparing the formulation as claimed in claim 1, which comprises thesteps of: a) mixing components a) and b) to give a homogeneouspremixture, and b) optionally introducing components c), d) and/or e).17. The use of the formulation as claimed in claim 1 in cosmeticformulations, in laundry detergents or for the surface treatment ofsubstrates.
 18. The use of the formulation as claimed in claim 1 forfiber treatment or fiber finishing.
 19. The use of the formulation asclaimed in claim 1 as a formulation for the treatment of textiles andother natural and synthetic fiberlike materials including paper.
 20. Theuse of the formulation as claimed in claim 1 as a softener. 21.(canceled)